CN101007277A - Catalyst for synthesis of indole and its preparation method - Google Patents
Catalyst for synthesis of indole and its preparation method Download PDFInfo
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Abstract
A catalyst for indole synthetic and the main active component is Ag; adjuvant is one or more of the following metals: Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, Zn, Cd, Mn, Tc, Re, Sc , Y, La, Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt; carrier chooses silicon dioxde, MCM-41 molecular sieve, SBA-15 control-hole materials, active carbon or aluminum oxide; the weight percentage of main active component is 1-30.0%, the weight percentage of adjuvant is 0.01-10%; specific surface area of carrier is 100-500m2/g, content of hole is 0.3-2.0cm3/g, bore diameter is 5-1000. Its preparation method is: dipping the soluble salt water solution of main active component and adjuvant on carrier, drying under 80-150DEG C, roasting under 200-550DEG C, deacidizing under 20-600DEG C.
Description
Technical field
The present invention relates to a kind of is the catalyst of raw material one-step method heterogeneous catalysis synthesis of indole with aniline and ethylene glycol.
The invention still further relates to above-mentioned Preparation of catalysts method.
Background technology
Indoles is the important source material of preparation medicine, agricultural chemicals, spices, dyestuff and feed addictive, is important heterocycle fine-chemical intermediate.The production capacity in the whole world is 7000t/a at present.Along with the development of its application study, derive the medicine and the agricultural chemicals of many important high added values by it, particularly the market demand of indole derivatives tryptophan increases rapidly at present, and only this item whole world distant view demand is at 100000t/a.Therefore, the market prospects of indoles are very wide.
Present industrial main employing ortho-chlorotolu'ene multistep processes synthesis of indole.Ortho-chlorotolu'ene makes dihydroindole through chlorination, cyaniding, ammonification, dehydration, then dehydrogenation and indoles.Because synthesis step is various, separation process is numerous and diverse, and energy consumption is big, the cost height, and produce a large amount of discarded objects in the preparation process and cause environmental pollution.The at present main method of using this backwardness of China is produced indoles, and meanwhile, China has successfully realized the industrialization of indoles secondary colour propylhomoserin now, the new technology of the synthesis of indole of therefore, be badly in need of that the technology that substitutes is simple, environmental friendliness and cost are inexpensive.
With aniline and ethylene glycol be raw material heterogeneous catalysis One Step Synthesis of Indole not only cost of material is cheap, production cost is low, operating procedure is simple, environmental friendliness has tangible advantage, is that synthesis of indole is the most promising a kind of.And the technology of this technology key is exactly a Study of Catalyst, and the eighties in 20th century, Japan carried out a large amount of correlative studys to this catalyst.
Catalyst such as discovery Cd, Cu, Ag and Zn such as Masuda all have certain activity (United States Patent (USP) 4436917) to the reaction of aniline and ethylene glycol One Step Synthesis of Indole.Under 350 ℃, normal pressure, in the fixed bed reaction yield of indoles all more than 20% (because of aniline excessive, in ethylene glycol), Ag/SiO wherein
2The indoles yield of-ZnO catalyst reaches more than 40%.But a main problem is also found in experiment: catalyst is at a few hours inactivation, and the yield straight line descends.This mainly is because aniline and indoles all contain the N atom that has lone pair electrons, and the chemisorbed of these materials on catalyst is strong especially, is difficult to desorption, is easy to cause the catalyst carbon deposition inactivation.
T. Honda etc. developed Ag-Co/SiO in 1989
2-ZnO catalyst (European patent 0427287).He at first prepares specific surface with waterglass and zinc nitrate coprecipitation is 240m
2The SiO of/g
2-ZnO carrier soaks method back loading 0.6%Co of elder generation and 11%Ag with dividing then, makes Ag-Co/SiO
2-ZnO catalyst.The result shows, under 1.0MPa, 375 ℃ of conditions, and in fixed bed reactors, Ag-Co/SiO
2The yield of aniline and ethylene glycol One Step Synthesis of Indole reaches 78% on-the ZnO catalyst, and the stability of catalyst is relatively good simultaneously.And this catalyst can pass through charcoal regeneration, and the performance of regeneration rear catalyst is constant substantially.
Recently, domesticly also begin to have carried out this research.Bibliographical information (catalysis journal 2003 Vol.24 No.6 471～474) infusion process has been developed Ag/SiO
2And Cu/SiO
2Catalyst, and investigated the catalytic performance of aniline, ethylene glycol One Step Synthesis of Indole.The indoles yield of two kinds of catalyst can reach about 80%, but the very fast inactivation of catalyst, and the yield that reacts 3 hours rear catalysts descends a lot.
To sum up, the catalyst of aniline, ethylene glycol One Step Synthesis of Indole has possessed good basis, wherein Ag-Co/SiO through the research in two, 30 years
2-ZnO catalyst has good active, selectivity and stability.Yet, Ag-Co/SiO
2-ZnO catalyst preparation technology more complicated at first will prepare SiO through quite complicated waterglass and zinc nitrate coprecipitation
2-ZnO carrier, and then prepare Ag-Co/SiO with step impregnation method
2-ZnO catalyst.And numerous and diverse preparation technology causes the cost of catalyst also quite expensive.The simple infusion process of domestic employing preparation technology has been developed Ag/SiO
2And Cu/SiO
2Catalyst, catalyst preparation process is simple, but the stability of catalyst is poor, and industrial applicability is not strong.
Summary of the invention
The object of the present invention is to provide a kind of catalyst of synthesis of indole.
Another purpose of the present invention is to provide a kind of method for preparing above-mentioned catalyst.
For achieving the above object, catalyst provided by the invention is made up of main active component, auxiliary agent and carrier three parts, and main active component is Ag; One or more of the following metal of selection of auxiliary: the Li of IA family, Na, K, Rb, Cs, the Be of IIA family, Mg, Ca, Sr, Ba, the Zn of IIB family, Cd, the Mn of VIIB family, Tc, Re, the Sc of IIIB family, Y, La system, the Fe of VIII family, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt, preferably Zn, Co, Pd are or/and Ir.Carrier is selected silica, MCM-41 molecular sieve, SBA-15 control hole material, active carbon or alundum (Al, preferably silica for use; Wherein:
Main active component A g accounts for 1～30.0% in total catalyst weight, and preferred 5～20%.
Auxiliary agent accounts for 0.01～10% in total catalyst weight.
The specific area of carrier is at 100～500m
2/ g, pore volume 0.3～2.0cm
3/ g, pore-size distribution are at 5～1000 , and preferred carrier specific surface is 150～450m
2/ g, pore volume are 0.5～1.0cm
3/ g, pore-size distribution are 50～500 .
The method of the above-mentioned catalyst of preparation provided by the invention, adopt co-impregnation or step impregnation method to be immersed on the carrier aqueous solution of the soluble-salt (as nitrate, hydrochloride, carbonate or oxalates) of main active component and auxiliary agent, 80～150 ℃ of dryings, 200～750 ℃ of roastings, 20～600 ℃ of reduction, external reduction or in-situ reducing method are adopted in reduction.The reducing agent that reduction is adopted is formaldehyde, hydrazine hydrate, H
2, or N
2+ H
2Gaseous mixture.
The infusion process that the present invention adopts is with commercially available high-ratio surface, the SiO of macropore
2Carrier as catalyst.Then with the main active component of catalyst and auxiliary agent to soak altogether or to divide the method for soaking to be impregnated on the carrier.Can save complicated coprecipitation like this and prepare SiO
2This step of-ZnO carrier.Another key of this method is to select the activity and the selectivity of proper auxiliary agent regulating catalyst for use, especially pays attention to the stability of modulation, raising catalyst.The catalytic activity of the catalyst of the present invention's development, selectivity and stability have very strong industrial application value than higher like this, and the Preparation of catalysts simple and reliable process, and the cost of catalyst is also relatively low.
Use above method, at SiO
2Last impregnated catalyst active component development SiO
2The Ag that supports is catalyst based, in fixed bed reactors, carry out the reaction of continuous aniline and ethylene glycol one-step method heterogeneous catalysis synthesis of indole, the discovery catalytic perfomance is higher, generate the conversion ratio 96.2% of indoles, the selectivity that generates indoles can reach 84.1%, and the yield that generates indoles can reach 81.1%.Wherein, the yield of the selectivity of generation indoles and generation indoles is all than Ag-Co/SiO
2The respective performances of-ZnO catalyst is slightly high, and, investigated discovery in the experiment 500 hour life-span, catalyst performance of the present invention is more stable, has very strong industrial application value.
Use catalyst of the present invention in fixed bed continuous reactor, to carry out.Technological process is simple, and the production efficiency height is easy to operate.Its typical operating condition is: reaction temperature: 300～450 ℃, and reaction pressure: 0.1～5.0MPa; The temperature of preheater: 200～400 ℃, aniline and ethylene glycol mixture material mol ratio be 10: 1, the charging air speed of aniline and ethylene glycol mixture material is: 0.1～2.0h
-1, water charging air speed is 0.05～1.0h
-1, the air speed of hydrogen is 50～1000h
-1
The specific embodiment
Below further be described by example.
Example 1
Development 5%Ag/SiO
2Catalyst (being labeled as catalyst 1).The preparation method is as follows: take by weighing 20 gram silica gel.Preparation contains the AgNO of 0.1 gram Ag/ml solution
3Aqueous solution 10ml adds in the above-mentioned carrier by infusion process, air dry, and 120 ℃ of oven dryings 4 hours, 350 ℃ of muffle furnace roastings 4 hours are at H
2Flow down in fixed bed and reduce, the condition of reduction is a normal pressure, 350 ℃, and air speed: 1200h
-1, 4h, reduce to preserve after the room temperature stand-by.
Example 2
Development 11%Ag/SiO
2Catalyst (being labeled as catalyst 2).The preparation method is as follows: take by weighing 20 gram silica gel.Preparation contains the AgNO of 0.1 gram Ag
3Aqueous solution 22ml adds in the above-mentioned carrier by infusion process, air dry, and 120 ℃ of oven dryings 4 hours, 350 ℃ of muffle furnace roastings 4 hours are at H
2Flow down in fixed bed and reduce, the condition of reduction is a normal pressure, 350 ℃, and air speed: 1200h
-1, 4h, reduce to preserve after the room temperature stand-by.
Example 3
Development 11%Ag5%Zn/SiO
2Catalyst (being labeled as catalyst 3).The preparation method is as follows: get 20 gram silica gel.Preparation contains the Zn (NO of 0.1 gram Zn
3)
2Aqueous solution 10ml adds in the carrier by infusion process, air dry, and 120 ℃ of oven dryings 4 hours, the ZnO/SiO that contains 5%Zn is made in 600 ℃ of muffle furnace roastings 4 hours
2(be labeled as 5%Zn/SiO
2) carrier, preparation contains the AgNO of 0.1 gram Ag
3Aqueous solution 22ml adds 5%Zn/SiO by infusion process
2In the carrier, air dry, 120 ℃ of oven dryings 4 hours, 350 ℃ of muffle furnace roastings 4 hours are at H
2Flow down in fixed bed and reduce, the condition of reduction is a normal pressure, 350 ℃, and air speed: 1200h
-1, 4h, reduce to preserve after the room temperature stand-by.
Example 4
Development 11%Ag5%Zn/SiO
2Catalyst (being labeled as catalyst 4).The preparation method is as follows: get 20 gram silica gel.Preparation contains the Zn (NO of 0.1 gram Zn
3)
2Aqueous solution 10ml adds in the above-mentioned carrier by infusion process, air dry, and 120 ℃ of oven dryings 4 hours, the ZnO/SiO that contains 5%Zn is made in 600 ℃ of muffle furnace roastings 4 hours
2(be labeled as 5%Zn/SiO
2) carrier, preparation contains the AgNO of 0.1 gram Ag
3Aqueous solution 22ml adds 5%Zn/SiO by infusion process
2In the carrier, air dry, 120 ℃ of oven dryings 4 hours, 4% hydrazine hydrate reduction is used in 350 ℃ of muffle furnace roastings 4 hours, uses the hydrazine hydrate of deionized water flush away remnants then, and 120 ℃ of dryings are stand-by.
Example 5
Development 11%Ag5%Zn0.3%K/SiO
2Catalyst (being labeled as catalyst 5).The preparation method is as follows: make the ZnO/SiO that contains 5%Zn by example 4
2(be labeled as 5%Zn/SiO
2) carrier.Preparation contains the KNO of 0.01 gram K
3Aqueous solution 6ml adds in the above-mentioned carrier by infusion process, air dry, and 120 ℃ of oven dryings 4 hours, the carrier that contains 5%Zn and 0.3%Co is made in 350 ℃ of muffle furnace roastings 4 hours.Preparation contains the AgNO of 0.1 gram Ag
3Aqueous solution 22ml adds 5%Zn0.3%K/SiO by infusion process
2In the carrier, air dry, 120 ℃ of oven dryings 4 hours, 350 ℃ of muffle furnace roastings 4 hours.Use 4% hydrazine hydrate reduction, use the hydrazine hydrate of deionized water flush away remnants then, 120 ℃ of dryings, stand-by.
Example 6
Development 11%Ag5%Zn0.5%Mg/Si0
2Catalyst (being labeled as catalyst 6).The preparation method is as follows: preparation contains the Zn (NO of 0.1 gram Zn respectively
3)
2Aqueous solution 10ml and the Mg (NO that contains 0.01 gram Mg
3)
2Aqueous solution 10ml joins in the silica gel by the method for soaking altogether, air dry, and 120 ℃ of oven dryings 4 hours, 5%Zn0.5%Mg/SiO is made in 350 ℃ of muffle furnace roastings 4 hours
2Carrier.Preparation contains the AgNO of 0.1 gram Ag
3Aqueous solution 22ml adds 5%Zn0.5%Mg/SiO by infusion process
2In the carrier, air dry, 120 ℃ of oven dryings 4 hours, 350 ℃ of muffle furnace roastings 4 hours.Use 4% hydrazine hydrate reduction, use the hydrazine hydrate of deionized water flush away remnants then, 120 ℃ of dryings, stand-by.
Example 7
Development 11%Ag5%Zn0.8%La/AC catalyst (this catalyst is labeled as catalyst 7).The preparation method is as follows: get 20 gram active carbons (AC), preparation contains the Zn (NO of 0.1 gram Zn respectively
3)
2Aqueous solution 10ml and the La (NO that contains 0.01 gram La
3)
3Aqueous solution 16ml joins in the active carbon by the method for soaking altogether, air dry, and 90 ℃ of oven dryings 4 hours, the 5%Zn0.8La/AC carrier is made in roasting 4 hours under the Ar gas atmosphere in 350 ℃ of tube furnaces.Preparation contains the AgNO of 0.1 gram Ag
3Aqueous solution 22ml adds in the 5%Zn0.8%La/AC carrier by infusion process, air dry, 90 ℃ of oven dryings 4 hours, roasting 4 hours under the Ar gas atmosphere in 350 ℃ of tube furnaces.Use 4% hydrazine hydrate reduction, use the hydrazine hydrate of deionized water flush away remnants then, 90 ℃ of vacuum drying, stand-by.
Example 8
Development 11%Ag5%Zn0.5%Re/MCM-41 catalyst (being labeled as catalyst 8).The preparation method is as follows: get 20 gram MCM-41 molecular sieves, preparation contains the Zn (NO of 0.1 gram Zn respectively
3)
2Aqueous solution 10ml and contain 0.01 the gram NH
4ReO
4Aqueous solution 10ml, join in the MCM-41 molecular sieve by the method for soaking altogether, air dry, 120 ℃ of oven dryings 4 hours, the 5%Zn0.5%Re/MCM-41 carrier is made in 350 ℃ of muffle furnace roastings 4 hours.Preparation contains the AgNO of 0.1 gram Ag
3Aqueous solution 22ml adds in the 5%Zn0.5%Re/MCM-41 carrier by infusion process, air dry, 120 ℃ of oven dryings 4 hours, 350 ℃ of muffle furnace roastings 4 hours.Use 4% hydrazine hydrate reduction, use the hydrazine hydrate of deionized water flush away remnants then, 120 ℃ of dryings, stand-by.
Example 9
Development 11%Ag5%Zn0.6Co/SiO
2Catalyst (being labeled as catalyst 9).The preparation method is as follows: make the ZnO/SiO that contains 5%Zn by example 4
2(be labeled as 5%Zn/SiO
2) carrier.Preparation contains the Co (NO of 0.01 gram Co
3)
2Aqueous solution 12ml floods above-mentioned silica gel with this aqueous solution, air dry, and 120 ℃ of oven dryings 4 hours, the 5%Zn0.6%Co/SiO that contains 5%Zn and 0.6%Co is made in 350 ℃ of muffle furnace roastings 4 hours
2Carrier.Preparation contains the AgNO of 0.1 gram Ag
3Aqueous solution 22ml adds 5%Zn0.6%Co/SiO by infusion process
2In the carrier, air dry, 120 ℃ of oven dryings 4 hours, 350 ℃ of muffle furnace roastings 4 hours.Use 4% hydrazine hydrate reduction, use the hydrazine hydrate of deionized water flush away remnants then, 120 ℃ of dryings, stand-by.
Example 10
Development 11%Ag5%Zn0.2%Ir/SiO
2Catalyst (being labeled as catalyst 10).The preparation method is as follows: get the silica gel of 20 grams as using in the example 1, prepare 5%Zn/SiO by example 4 methods
2, preparation contains the AgNO of 0.1 gram Ag
3Aqueous solution 22ml divides with this aqueous solution and to flood above-mentioned 5%Zn/SiO three times
2, use above AgNO
3Aqueous solution dipping 5%Zn/SiO
2, air dry, 120 ℃ of oven dryings 4 hours, 350 ℃ of muffle furnace roastings 4 hours with one night of 4% hydrazine hydrate reduction of 200ml, are used the hydrazine hydrate of deionized water flush away remnants then, and 120 ℃ of dryings make 11%Ag5%Zn/SiO
2Preparation contains the H of 0.005 gram Ir
2IrCl
68 milliliters of the aqueous solution are with this aqueous solution dipping 11%Ag5%Zn/SiO
2, air dry, 120 ℃ of oven dryings 4 hours are used 4% hydrazine hydrate reduction, use deionized water flush away Cl then
-1With the hydrazine hydrate of remnants, 120 ℃ of dryings make 11%Ag5%Zn0.2%Ir/SiO
2Catalyst.
Example 11
Development 11%Ag5%Zn0.2%Pd/SiO
2Catalyst (being labeled as catalyst 11).The preparation method is as follows.Prepare 11%Ag5%Zn/SiO by example 4. methods
2Preparation contains the Pd (NO of 0.005 gram Pd
3)
28 milliliters of the aqueous solution are with this solution impregnation 11%Ag5%Zn/SiO
2, air dry, 120 ℃ of oven dryings 4 hours are used 4% hydrazine hydrate reduction, use the hydrazine hydrate of deionized water flush away remnants then, and 120 ℃ of dryings make 11%Ag5%Zn0.2%Pd/SiO
2Catalyst.
Example 12
Development 11%Ag5%Zn0.6%Co0.2%Ir0.2%Pd/SiO
2Catalyst (being labeled as catalyst 12).The preparation method is as follows.Press example 9 methods development 11%Ag5%Zn0.6%Co/SiO
2Preparation contains the H of 0.005 gram Ir respectively
2IrCl
68 milliliters of the aqueous solution and contain the Pd (NO of 0.005 gram Pd
3)
28 milliliters of the aqueous solution are with these two kinds of solution impregnation 11%Ag5%Zn0.6%Co/SiO
2, air dry, 120 ℃ of oven dryings 4 hours are used 4% hydrazine hydrate reduction, use deionized water flush away Cl then
-1With the hydrazine hydrate of remnants, 120 ℃ of dryings make 11%Ag5%Zn0.6%Co0.2%Ir0.2%Pd/SiO
2Catalyst.
Example 13
Development 20%Ag5%Zn0.6%Co0.2%Ir0.2%Pd/SiO
2Catalyst (being labeled as catalyst 13).The preparation method is as follows.Preparation contains the AgNO of 0.2 gram Ag respectively
3Aqueous solution 20ml, contain 0.01 the gram Co Co (NO
3)
2Aqueous solution 12ml, contain 0.1 the gram Zn Zn (NO
3)
2Aqueous solution 10ml joins in the silica gel by infusion process, air dry, and 120 ℃ of oven dryings 4 hours are used 4% hydrazine hydrate reduction, preparation 20%Ag5%Zn0.6%Co/SiO
2Preparation contains the H of 0.005 gram Ir respectively
2IrCl
68 milliliters of the aqueous solution and the Pd (NO that contains 0.005 gram Pd
3)
28 milliliters of the aqueous solution fully mix easily with above, with this mixed solution dipping 20%Ag5%Zn0.6%Co/SiO
2, air dry, 120 ℃ of oven dryings 4 hours are used 4% hydrazine hydrate reduction, use deionized water flush away Cl then
-1With the hydrazine hydrate of remnants, 120 ℃ of dryings make 20%Ag5%Zn0.6%Co0.2%Ir0.2%Pd/SiO
2Catalyst.
Example 14
Get 6ml catalyst in the example 1, the fixed bed reactors of packing into, the sealing back is at H
2Reduce in the stream, the condition of reduction be normal pressure, 350 ℃ the reduction 4 hours, H
2Air speed be 1200h
-1After the reduction temperature of reactor is risen to 375 ℃, reaction pressure rises to 1.0MPa, H
2Air speed be adjusted to 300h
-1, with mol ratio be 10: 1 aniline and ethylene glycol mixture material with accurate duplex plunger pump with 0.42h
-1Flow velocity is thrown in the preheater, and water is pressed 0.21h with accurate duplex plunger pump
-1Flow velocity is thrown in the preheater.Enter preheater hydrogen carry the aniline of vaporization and ethylene glycol and water secretly and enter and carry out catalytic reaction in the reactor.React 24 hours sample analysis, response data is listed in the table 1.
Example 15
Get 6ml catalyst in the example 2, the fixed bed reactors of packing into.Reduce and react by example 10 described methods.Response data is listed in the table 1.Aniline and ethylene glycol and water enter and carry out catalytic reaction in the reactor.Response data is listed in the table 1.
Example 16
Get 6ml catalyst in the example 3, the fixed bed reactors of packing into.Reduce and react by example 10 described methods.Response data is listed in the table 1.Aniline and ethylene glycol and water enter and carry out catalytic reaction in the reactor.Response data is listed in the table 1.
Example 17
Get 6ml catalyst in the example 4, the fixed bed reactors of packing into.Reduce and react by example 10 described methods.Response data is listed in the table 1.Aniline and ethylene glycol and water enter and carry out catalytic reaction in the reactor.Response data is listed in the table 1.
Example 18
Get 6ml catalyst in the example 5, the fixed bed reactors of packing into.Reduce and react by example 10 described methods.Response data is listed in the table 1.Aniline and ethylene glycol and water enter and carry out catalytic reaction in the reactor.Response data is listed in the table 1.
Example 19
Get 6ml catalyst in the example 6, the fixed bed reactors of packing into.Reduce and react by example 10 described methods.Response data is listed in the table 1.Aniline and ethylene glycol and water enter and carry out catalytic reaction in the reactor.Response data is listed in the table 1.
Example 20
Get 6ml catalyst in the example 7, the fixed bed reactors of packing into.Reduce and react by example 10 described methods.Response data is listed in the table 1.Aniline and ethylene glycol and water enter and carry out catalytic reaction in the reactor.Response data is listed in the table 1.
Example 21
Get 6ml catalyst in the example 8, the fixed bed reactors of packing into.Reduce and react by example 10 described methods.Response data is listed in the table 1.Aniline and ethylene glycol and water enter and carry out catalytic reaction in the reactor.Response data is listed in the table 1.
Example 22
Get 6ml catalyst in the example 9, the fixed bed reactors of packing into.Reduce and react by example 10 described methods.Response data is listed in the table 1.Aniline and ethylene glycol and water enter and carry out catalytic reaction in the reactor.Response data is listed in the table 1.
Example 23
Get 6ml catalyst in the example 10, the fixed bed reactors of packing into.Reduce and react by example 10 described methods.Response data is listed in the table 1.Aniline and ethylene glycol and water enter and carry out catalytic reaction in the reactor.Response data is listed in the table 1.
Example 24
Get 6ml catalyst in the example 11, the fixed bed reactors of packing into.Reduce and react by example 10 described methods.Response data is listed in the table 1.Aniline and ethylene glycol and water enter and carry out catalytic reaction in the reactor.Response data is listed in the table 1.
Example 25
Get 6ml catalyst in the example 12, the fixed bed reactors of packing into.Reduce and react by example 10 described methods.Response data is listed in the table 1.Aniline and ethylene glycol and water enter and carry out catalytic reaction in the reactor.Response data is listed in the table 1.
Example 26
Get 6ml catalyst in the example 13, the fixed bed reactors of packing into.Reduce and react by example 10 described methods.Response data is listed in the table 1.Aniline and ethylene glycol and water enter and carry out catalytic reaction in the reactor.Response data is listed in the table 1.
As can be known from Table 1,5%Ag/SiO
2The catalytic performance of aniline and ethylene glycol One Step Synthesis of Indole is relatively poor on the catalyst, and ethylene glycol conversion ratio, the selectivity that generates indoles and the yield of indoles are respectively 52.5%, 30.6% and 16.7%.11%Ag/SiO
2The ethylene glycol conversion ratio and the indoles yield of catalyst synthesis of indole all have bigger increase, show that an amount of increase Ag content helps the raising of catalyst performance, below the Ag content of all catalyst all be 11%.And the 11%Ag5%Zn/SiO of interpolation element Zn
2The indoles selectivity of catalyst synthesis of indole improves a lot, and reaches 41.1%.
Different catalysts preparation technology has certain influence to catalyst performance, and the influence of different catalysts method of reducing to catalyst performance compared in experiment.As seen use the 11%Ag5%Zn/SiO of 4% hydrazine hydrate reduction
2Every catalytic performance index of catalyst is all than H
2The 11%Ag5%Zn/SiO of 350 ℃ of reduction of normal pressure
2The catalyst index is slightly high, and convenient with 4% hydrazine hydrate reduction, and therefore following catalyst all adopts 4% hydrazine hydrate reduction catalyst.
Different carriers has certain influence to the performance of synthesis of indole, SiO
2The catalyst that supports has preferable activity and selectivity.
The effects the influence of several auxiliary agents, find that several different auxiliary agents have all improved the selectivity and the yield of the synthesis of indole of catalyst in various degree.Wherein, the catalyst performance that adds alkali metal K and interpolation alkaline-earth metal Mg improves a lot, and add selectivity and the yield that the Co auxiliary agent can improve the synthesis of indole of catalyst greatly, add the performance that Ir and Pd auxiliary agent can improve catalyst to a certain extent.And these three kinds of different auxiliary agents are all added in the catalyst, find that the performance of catalyst improves a lot, ethylene glycol conversion ratio, the selectivity that generates indoles and the yield of indoles are respectively 96.2%, 84.3% and 81.1%.This result is comparable to the best result of Japan's report.
The performance that has compared the catalyst of two kinds of distinct methods developments of step impregnation method and co-impregnation.As seen the performance of the catalyst of step impregnation method development will be a little more than the performance of the catalyst of co-impregnation development.But co-impregnation has the simple more advantage of preparation technology.
Above the present invention has adopted comparatively simple infusion process development SiO
2The Ag that supports is catalyst based, by add multiple different additive modification catalyst in catalyst, has prepared the synthesis of indole catalyst with high activity, high selectivity and high stability, and it is catalyst based to have developed the heterogeneous Ag with distinct characteristic.
The catalytic performance of table 1 different catalysts
| Sequence number | Catalyst is formed | Ethylene glycol conversion ratio (%) | Indoles selectivity (%) | Indoles yield (%) |
| Catalyst 1 | 5％Ag/SiO 2 * | 52.5 | 30.6 | 16.7 |
| Catalyst 2 | 11％Ag/SiO 2 * | 98.9 | 26.4 | 26.1 |
| Catalyst 3 | 11％Ag5％Zn/SiO 2 * | 89.3 | 41.1 | 36.7 |
| Catalyst 4 | 11％Ag5％Zn/SiO 2 | 91.3 | 43.5 | 39.7 |
| Catalyst 5 | 11％Ag5％Zn0.3％K/SiO 2 | 98.8 | 58.5 | 57.8 |
| Catalyst 6 | 11％Ag5％Zn0.5％Mg/SiO 2 | 96.3 | 59.4 | 57.2 |
| Catalyst 7 | 11％Ag5％Zn0.8％La/AC | 78.6 | 46.5 | 36.5 |
| Catalyst 8 | 11％Ag5％Zn0.5％Re/MCM-41 | 95.7 | 40.3 | 38.6 |
| Catalyst 9 | 11％Ag5％Zn0.6％Co/SiO 2 | 95.7 | 68.5 | 65.5 |
| Catalyst 10 | 11％Ag5％Zn0.2％Ir/SiO 2 | 92.1 | 54.3 | 50.0 |
| Catalyst 11 | 11％Ag5％Zn0.2％Pd/SiO 2 | 90.6 | 56.1 | 50.8 |
| Catalyst 12 | 11％Ag5％Zn0.6％Co0.2％Ir0.2％Pd/SiO 2 | 96.2 | 84.3 | 81.1 |
| Catalyst 13 | 20％Ag5％Zn0.6％Co0.2％Ir0.2％Pd/SiO 2 | 98.5 | 79.3 | 78.1 |
Reaction pressure: 1.0MPa; Temperature: 375 ℃; Aniline and ethylene glycol air speed: 0.42h
-1Water air speed: 0.21h
-1H
2Air speed 300h
-1Reaction time: 24 hours
*Adopt H in the catalyst preparation process process
2350 ℃ of reduction of normal pressure, other catalyst all adopts 4% hydrazine hydrate reduction.
Claims (10)
1. the catalyst of a synthesis of indole is made up of main active component, auxiliary agent and carrier three parts, and main active component is Ag; One or more of the following metal of selection of auxiliary: the Li of IA family, Na, K, Rb, Cs, the Be of IIA family, Mg, Ca, Sr, Ba, the Zn of IIB family, Cd, Mn, Tc, the Re of VII B family, the Sc of IIIB family, Y, La system, the Fe of VIII family, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt; Carrier is selected silica for use, MCM-41 molecular sieve, SBA-15 control hole material, active carbon or alundum (Al; Wherein:
Main active component A g accounts for 1～30.0% in total catalyst weight, each auxiliary agent accounts for 0.01～10.0% in total catalyst weight, and all auxiliary agent weight sums account for 0.05～15% in total catalyst weight;
The specific area of carrier is at 100～500m
2/ g, pore volume 0.3～2.0cm
3/ g, pore-size distribution is at 5～1000 .
2. catalyst as claimed in claim 1 is characterized in that main active component A g accounts for 5～20% in total catalyst weight.
3. catalyst as claimed in claim 1, it is characterized in that auxiliary agent is one or more among Li, Na, K, Rb, Cs, IIA, Be, Mg, Ca, Sr, Ba, Zn, Cd, Mn, Tc, Re, Sc, Y, La system, Fe, Co, Ni, Ru, Rh, Pd, Os, Ir and the Pt.
4. catalyst as claimed in claim 1 is characterized in that, carrier is silica, MCM-41 molecular sieve, SBA-15 control hole material, active carbon or alundum (Al.
5. catalyst as claimed in claim 1 is characterized in that, the carrier specific surface is 150～450m
2/ g, pore volume are 0.5～1.0cm
3/ g, pore-size distribution are 50～500 .
6. method for preparing the described catalyst of claim 1 is immersed on the carrier 80～150 ℃ of dryings, 200～750 ℃ of roastings, 20～600 ℃ of reduction with the aqueous solution of the soluble-salt of main active component and auxiliary agent.
7. method as claimed in claim 6 is characterized in that, main active component and auxiliary agent are to adopt co-impregnation or step impregnation method to be immersed on the carrier.
8. method as claimed in claim 6 is characterized in that, reduction is to adopt external reduction or in-situ reducing method.
9. method as claimed in claim 6 is characterized in that, the reducing agent that reduction is adopted is formaldehyde, hydrazine hydrate, H
2, or N
2+ H
2Gaseous mixture.
10. method as claimed in claim 6 is characterized in that, the soluble-salt of main active component and auxiliary agent is solubility salts such as nitrate, hydrochloride, carbonate, oxalates.
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| CN100418625C CN100418625C (en) | 2008-09-17 |
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| CN101822984A (en) * | 2010-05-11 | 2010-09-08 | 太原理工大学 | Catalyst for synthetizing indole and preparation method thereof |
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| JPS5923306B2 (en) * | 1980-06-03 | 1984-06-01 | 三井東圧化学株式会社 | Method for producing indole or indole derivatives |
| US4456760A (en) * | 1981-04-15 | 1984-06-26 | Mitsui Toatsu Chemicals, Incorporated | Process for the preparation of indoles |
| JPS5835171A (en) * | 1981-08-25 | 1983-03-01 | Mitsui Toatsu Chem Inc | Improved method for preparation of indole |
| US4727161A (en) * | 1984-11-19 | 1988-02-23 | Mitsui Toatsu Chemicals, Incorporated | Process for the preparation of indoles |
| JPS61151171A (en) * | 1984-12-26 | 1986-07-09 | Mitsui Toatsu Chem Inc | Production of indole |
| JPH03218351A (en) * | 1989-11-10 | 1991-09-25 | Mitsui Toatsu Chem Inc | Preparation of indoles |
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