CN104667924A - Catalyst for preparing 1,3-propylene glycol by employing glycerin hydrogenation and preparation method of 1,3-propylene glycol - Google Patents
Catalyst for preparing 1,3-propylene glycol by employing glycerin hydrogenation and preparation method of 1,3-propylene glycol Download PDFInfo
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Abstract
The invention provides a catalyst for preparing 1,3-propylene glycol by employing glycerin hydrogenation and a preparation method of the 1,3-propylene glycol. Particularly, SiO2 or an HZSM-5 molecular sieve is taken as a carrier; Re and Ir as taken as main active components; and the main active components Re and Ir are simultaneously loaded on the carrier or are loaded on the carrier according to an order of firstly loading Re and then loading Ir by adopting an impregnation method. By virtue of the catalyst provided by the invention in the reaction of preparing the 1,3-propylene glycol by employing the glycerin hydrogenation, the glycerin can be converted into the 1,3-propylene glycol with high activity and high selectivity under the conditions of certain temperature and hydrogen pressure.
Description
Technical field
The present invention relates to a kind of Catalysts and its preparation method for preparing 1,3-propylene glycol by hydrogenation of glycerin.
Background technology
1,3-PD is the important source material of producing PTT.Existing 1,3-PD technology of preparing has methacrylaldehyde aquation hydrogenation method, oxirane carbonyl hydrogenation method and microbe fermentation method and directly hydrogenizing glycerol method.
CN96198050.8 discloses a kind of oxirane carbonyl hydrogenation legal system 1, the technology of ammediol, oxirane and synthesis gas are reacted under catalyst existent condition and generate 3-HPA, 3-HPA and hydrogen react and generate 1,3-PD under catalyst existent condition.
CN93114516.3 discloses a kind of dehydrating glycerin through methacrylaldehyde aquation hydrogenation legal system 1, the technology of ammediol, glycerine is dewatered under catalyst existent condition and generates methacrylaldehyde, methacrylaldehyde generates 3-HPA through hydration reaction, 3-HPA and hydrogen react and generate 1,3-PD under catalyst existent condition.
CN02100233.9 discloses a kind of formaldehyde and acetaldehyde condensation through 3-HPA hydrogenation legal system 1, the technology of ammediol, by formaldehyde and acetaldehyde condensation generation 3-HPA in the basic conditions, 3-HPA and hydrogen react and generate 1,3-PD under catalyst existent condition.
Above-mentioned technical matters is more loaded down with trivial details, severe reaction conditions, and problem of environmental pollution is also more serious.
It is the technology that substrate adopts microbe fermentation method synthesis 1,3-PD that document (modern chemical industry, 2002,22 (7): 34) reports with glycerine.Because product is the aqueous solution that concentration is very low, production efficiency is lower.
Document (Catalysis Communication9 (2008) 1360-1363) reports a kind of glycerine hydrogenation and directly makes 1, the method of ammediol is wherein solvent with DMI, by making 1, ammediol and hydrogen and specific catalyst exposure also remove a hydroxyl and obtain 1,3-PD, but accessory substance 1,2-propane diols is more, and target product 1,3-PD is selective lower, make the economy of this technical process lower.
Document (Applied Catalysis A:General433-434 (2012) 128-134) reports the method for the direct 1,3-PD processed of a kind of glycerine hydrogenation, adopts batch tank reactor, Ir-ReOx/SiO
2for catalyst, but the problem of preparation method due to catalyst, obtained Ir-ReOx/SiO
2the activity of catalyst own is very low, needs to add H in reaction system
2sO
4or HZSM-5 acidic molecular sieve is that co-catalyst could obtain good result; And catalyst needs, through independent reduction treatment, then could add H before use
2sO
4or HZSM-5 acidic molecular sieve is that co-catalyst uses.H
2sO
4can bring equipment corrosion and environmental issue, and above-mentioned technical operation is loaded down with trivial details.
The process of the direct 1,3-PD processed of glycerine hydrogenation is simple, and cheaper starting materials is easy to get, and has development prospect.In order to enable the process of the direct 1,3-PD processed of glycerine hydrogenation meet the requirement of industrial production to production cost, must improve further on prior art basis, the economy of process is improved.
To sum up, existing 1,3-PD technology of preparing has acrolein hydration hydrogenation method, oxirane carbonyl hydrogenation method and microbe fermentation method and directly hydrogenizing glycerol method.Wherein, acrolein hydration hydrogenation method and oxirane carbonyl hydrogenation method belong to indirect hydrogenation method, and technics comparing is loaded down with trivial details; Microbe fermentation method due to product be the aqueous solution that concentration is very low, efficiency is lower; Directly hydrogenizing glycerol method is the 1,3-PD novel preparation method be just developed recent years, and the method can obtain 1,3-PD or 1,2-PD by making 1,3-PD hydrogenation and removing hydroxyl on specific catalyst, has development prospect.But according to the result of study of open report, still there is some problems in existing directly hydrogenizing glycerol 1,3-PD catalyst technology, can not meet industrial requirement.
Summary of the invention
The invention provides a kind of preparing 1,3-propylene glycol by hydrogenation of glycerin catalyst, compared with prior art, have employed the catalyst technology of less expensive, environmental protection, and process is simple, makes glycerine optionally be converted into 1,3-PD at certain temperature and Hydrogen Vapor Pressure condition.
For this reason, the invention provides a kind of catalyst for preparing 1,3-propylene glycol by hydrogenation of glycerin, it is characterized in that, described catalyst is with SiO
2or HZSM-5 molecular sieve is carrier, with Re and Ir for main active component, wherein said main active component Re and Ir is carried on described carrier by infusion process simultaneously or by the order of first load Re load Ir again.
In a preferred embodiment, based on the gross weight of described catalyst, in described catalyst, the content of each component is: the content of Re is the content of 0.2% ~ 5.0%, Ir is 0.2% ~ 5.0%, and all the other are described carrier.
In a preferred embodiment, described catalyst is also containing adjuvant component.Preferably, described adjuvant component is one or more in Al, Zn, P, Mg, Zr and W.
In a preferred embodiment, based on the gross weight of described catalyst, in described catalyst, the content of each component is: the content of Re is the content of 0.2% ~ 5.0%, Ir is 0.2% ~ 5.0%, the content of described adjuvant component is 0.01% ~ 0.05%, and all the other are described carrier.
It is above-mentioned for glycerine hydrogenation system 1 that the present invention also provides one to prepare, the method of the catalyst of ammediol, it is characterized in that, described method comprises be carried on described carrier by described main active component Re and Ir by co-impregnation simultaneously, and wherein said co-impregnation comprises: (a) is by the solution of composition preparation containing Re and Ir of described catalyst; The b SiO of solution impregnation as described carrier containing Re and Ir that () obtains by composition step (a) of described catalyst
2or HZSM-5 molecular sieve, finally carry out drying and roasting.
It is above-mentioned for glycerine hydrogenation system 1 that the present invention also provides one to prepare, the method of the catalyst of ammediol, it is characterized in that, described method comprises and is carried on described carrier by described main active component Re and Ir successively by step impregnation method, and wherein said step impregnation method comprises: (a) is by solution containing Re of the composition preparation of described catalyst and with the SiO of gained solution impregnation as described carrier
2or HZSM-5 molecular sieve, then drying also carries out roasting alternatively; B (), by the composition preparation of described catalyst containing the solution of Ir, the described carrier containing Re component after the solution impregnation drying containing Ir that (c) obtains by step (b) and/or roasting, finally carries out drying also roasting.
It is above-mentioned for glycerine hydrogenation system 1 that the present invention also provides one to prepare, the method of the catalyst of ammediol, it is characterized in that, described adjuvant component is carried on described carrier by infusion process, wherein first by composition carrier described in the solution impregnation containing described adjuvant component of described catalyst, then dry and carry out roasting alternatively, then by main active component described in the method load of main active component described in aforementioned load.
In a preferred embodiment, the temperature of described drying is 90 ~ 150 DEG C and the time is 2 ~ 15 hours, and the temperature of described roasting is 200 ~ 950 DEG C and the time is 2 ~ 10 hours.
In a preferred embodiment, the described solution containing Re is rehenic acid aqueous ammonium; The described solution containing Ir is the chloro-iridic acid aqueous solution; The described solution containing adjuvant component is the mixture of one or more in aluminum nitrate aqueous solution, zinc nitrate aqueous solution, phosphate aqueous solution, magnesium nitrate aqueous solution, the zirconium nitrate aqueous solution, zirconyl nitrate solution and ammonium metatungstate aqueous solution.
Detailed description of the invention
According to the catalyst for preparing 1,3-propylene glycol by hydrogenation of glycerin of the present invention, it is with SiO
2or HZSM-5 molecular sieve is carrier, the main active component of catalyst is Re and Ir, Re and Ir wherein as main active component is carried on SiO preferably by co-impregnation simultaneously
2or on HZSM-5 carrier, or also by the first load Re component of step impregnation method load Ir component again, finally can carry out drying and roasting.
According to the catalyst for preparing 1,3-propylene glycol by hydrogenation of glycerin of the present invention, when main active component Re and Ir is carried on SiO by co-impregnation simultaneously
2or time on HZSM-5 molecular sieve carrier, described catalyst is preferably prepared according to following step: (a) is by the mixed solution of composition preparation containing a certain amount of Re and a certain amount of Ir of catalyst; B () floods a certain amount of carrier S iO by the mixed solution that composition step (a) of catalyst obtains
2or HZSM-5 molecular sieve, finally carry out drying and roasting, thus obtained described catalyst.
Alternatively, according to the catalyst for preparing 1,3-propylene glycol by hydrogenation of glycerin of the present invention, when main active component Re and Ir is carried on SiO by step impregnation method
2or time on HZSM-5 molecular sieve carrier, first load Re component load Ir component again, described catalyst is preferably prepared according to following step: (a) also uses by the solution of composition preparation containing a certain amount of Re of catalyst a certain amount of carrier S iO of solution impregnation obtained
2or HZSM-5, then dry or roasting further; B (), by the solution of composition preparation containing a certain amount of Ir of catalyst, (c) obtains the SiO containing Re component after drying and/or roasting by solution impregnation step (a) of step (b)
2or HZSM-5 carrier, finally carry out drying and roasting, thus obtained described catalyst.
According to the catalyst for preparing 1,3-propylene glycol by hydrogenation of glycerin of the present invention, based on the gross weight of described catalyst, in catalyst, the content of each component is preferably: the content of Re is the content of 0.2% ~ 5.0%, Ir is 0.2% ~ 5.0%, and all the other are SiO
2or HZSM-5 molecular sieve carrier.
According to the catalyst for preparing 1,3-propylene glycol by hydrogenation of glycerin of the present invention, except containing SiO
2or HZSM-5 molecular sieve is carrier and is outside main active component containing Re and Ir, can also contain one or more adjuvant components.
Preferably, when the catalyst for preparing 1,3-propylene glycol by hydrogenation of glycerin according to the present invention contains adjuvant component, described catalyst can be prepared according to following step: (a) is by the solution of composition preparation containing a certain amount of adjuvant component of catalyst; B a certain amount of SiO of solution impregnation that () obtains by composition step (a) of catalyst
2or HZSM-5 molecular sieve carrier, then dry also roasting; (c) by the composition preparation of catalyst containing the mixed solution of a certain amount of Re and a certain amount of Ir, and with the SiO containing adjuvant component that this solution impregnation step (b) obtains
2or HZSM-5 molecular sieve carrier, final drying roasting, thus obtained described catalyst.
Alternatively, when the catalyst for preparing 1,3-propylene glycol by hydrogenation of glycerin according to the present invention contains adjuvant component, described catalyst can also be prepared according to following step: (a) is by the solution of composition preparation containing a certain amount of adjuvant component of catalyst; B a certain amount of SiO of solution impregnation that () obtains by composition step (a) of catalyst
2or HZSM-5 molecular sieve carrier, then dry also roasting; (c) by the composition preparation of catalyst containing the solution of a certain amount of Re, and with the SiO containing adjuvant component that this solution impregnation step (b) obtains
2or HZSM-5 molecular sieve carrier, then dry or roasting further; (d) by the composition preparation of catalyst containing the solution of a certain amount of Ir, and with the SiO containing adjuvant component and Re that this solution impregnation step (c) obtains
2or HZSM-5 molecular sieve carrier, final drying roasting, thus obtained described catalyst.
According to the catalyst for preparing 1,3-propylene glycol by hydrogenation of glycerin of the present invention, when containing adjuvant component in catalyst, described adjuvant component is preferably one or more in Al, Zn, P, Mg, Zr and W.
According to of the present invention for glycerine hydrogenation system 1, the catalyst of ammediol, when containing adjuvant component in catalyst, based on the gross weight of described catalyst, in described catalyst, the content of each component is preferably: the content of Re is 0.2% ~ 5.0%, the content of Ir is 0.2% ~ 5.0%, and the content of adjuvant component is 0.01% ~ 0.05%, and all the other are SiO
2or HZSM-5 molecular sieve carrier.
According to the catalyst for preparing 1,3-propylene glycol by hydrogenation of glycerin of the present invention, preferably, in the preparation process of described catalyst, the solution containing Re of use can be rehenic acid aqueous ammonium; Solution containing Ir can be the chloro-iridic acid aqueous solution; Solution containing adjuvant component can be one or more the mixture in aluminum nitrate aqueous solution, zinc nitrate aqueous solution, phosphate aqueous solution, magnesium nitrate aqueous solution, zirconium nitrate or zirconyl nitrate solution, ammonium metatungstate aqueous solution.
According to the catalyst for preparing 1,3-propylene glycol by hydrogenation of glycerin of the present invention, wherein as the SiO of carrier
2can be Bio-sil that is commercial or that prepare according to conventional methods, and such silica gel can be powder, spherical or irregular particle.The average pore size of preferred silica gel is 0.6 ~ 2.0nm, and specific area is 150 ~ 600m
2/ g, pore volume is 0.4 ~ 1.3ml/g.
According to the catalyst for preparing 1,3-propylene glycol by hydrogenation of glycerin of the present invention, the HZSM-5 molecular sieve as carrier can be the commercial or HZSM-5 molecular sieve prepared according to conventional methods, and it can be powder, spherical, bar shaped or irregular particle.SiO in preferred HZSM-5 molecular sieve
2/ Al
2o
3be 20 ~ 300.
According to of the present invention in the catalyst preparation process of preparing 1,3-propylene glycol by hydrogenation of glycerin, described drying and roasting can be carried out according to conventional methods under air or inert atmosphere.Preferably, the temperature of described drying is 90 ~ 150 DEG C, 2 ~ 15 hours drying times.The temperature of described roasting is 200 ~ 950 DEG C, roasting time 2 ~ 10 hours.
Provided by the invention for glycerine hydrogenation system 1, the catalyst of ammediol, may be used for being converted into 1,3-PD by glycerine high activity and highly selective at certain temperature and Hydrogen Vapor Pressure condition, directly hydrogenizing glycerol 1,3-PD process is made to have better economy.
According to provided by the invention for glycerine hydrogenation system 1, the catalyst of ammediol, when being used for preparing 1,3-propylene glycol by hydrogenation of glycerin process by described catalyst, batch tank reactor process or continuous-flow paste state bed reactor can be adopted, also can adopt continuous fixed bed reactor technique.Wherein preferred continuous fixed bed reactor technique.
Below by specific embodiment and comparative example, the present invention will be further described, but the present invention is not limited to these embodiments.
Embodiment 1
Catalyst is Ir/Re/SiO
2, the weight of catalyst consists of: Ir is 1%, Re is 1%, and all the other are carrier S iO
2.
This catalyst is prepared by following step: (a) contains the rehenic acid aqueous ammonium dipping 9.8g SiO of 0.1g Re with 15ml
2, then 120 DEG C of dryings 4 hours; The b SiO containing Re component that () obtains with chloro-iridic acid aqueous impregnation step (a) that 15ml contains 0.1g Ir
2, then 120 DEG C of dryings 4 hours, then 500 DEG C of roastings 4 hours, obtained described catalyst.
Embodiment 2
Catalyst is Ir/Re/SiO
2, the weight of catalyst consists of: Ir is 2%, Re is 2%, and all the other are carrier S iO
2.
This catalyst is prepared by following step: (a) contains the rehenic acid aqueous ammonium dipping 9.6g SiO of 0.2g Re with 15ml
2, then 120 DEG C of dryings 4 hours; The b SiO containing Re component that () obtains with chloro-iridic acid aqueous impregnation step (a) that 15ml contains 0.2g Ir
2, then 120 DEG C of dryings 4 hours, then 500 DEG C of roastings 4 hours, obtained described catalyst.
Embodiment 3
Catalyst is Ir/Re/SiO
2, the weight of catalyst consists of: Ir is 2%, Re is 2%, and all the other are carrier S iO
2.
This catalyst is prepared by following step: (a) contains the rehenic acid aqueous ammonium dipping 9.6g SiO of 0.2g Re with 15ml
2, then 120 DEG C of dryings 4 hours, then 500 DEG C of roastings 4 hours; The b SiO containing Re component that () obtains with chloro-iridic acid aqueous impregnation step (a) that 15ml contains 0.2g Ir
2, then 120 DEG C of dryings 4 hours, then 500 DEG C of roastings 4 hours, obtained described catalyst.
Embodiment 4
Catalyst is Ir-Re/SiO
2, the weight of catalyst consists of: Ir is 2%, Re is 2%, and all the other are carrier S iO
2.
This catalyst is prepared by following step: (a) prepares 15ml containing the rehenic acid ammonium of 0.2g Re and 0.2g Ir and the mixed aqueous solution of chloro-iridic acid; B aqueous impregnation 9.6g SiO that () obtains by step (a)
2, then 120 DEG C of dryings 4 hours, then 500 DEG C of roastings 4 hours, obtained described catalyst.
Embodiment 5
Catalyst is Ir/Re/Al/SiO
2, the weight of catalyst consists of: Ir is 2%, Re be 2%, Al is 0.03%, and all the other are carrier S iO
2.
This catalyst is prepared by following step: (a) contains the aluminum nitrate aqueous solution dipping 9.597g SiO of 0.003g Al with 15ml
2, then 120 DEG C of dryings 4 hours, then 700 DEG C of roastings 4 hours; The b SiO that impregnated of Al component that () obtains with rehenic acid aqueous ammonium impregnation steps (a) that 15ml contains 0.2g Re
2, then 120 DEG C of dryings 4 hours; The c SiO containing Re and Al that () obtains with chloro-iridic acid aqueous impregnation step (b) that 15ml contains 0.2g Ir
2, then 120 DEG C of dryings 4 hours, then 500 DEG C of roastings 4 hours, obtained described catalyst.
Embodiment 6
Catalyst is Ir/Re/P/SiO
2, the weight of catalyst consists of: Ir is 2%, Re be 2%, P is 0.03%, and all the other are carrier S iO
2.
This catalyst is prepared by following step: (a) contains the phosphate aqueous solution dipping 9.597g SiO of 0.003g P with 15ml
2, then 120 DEG C of dryings 4 hours, then 700 DEG C of roastings 4 hours; The b SiO that impregnated of P component that () obtains with rehenic acid aqueous ammonium impregnation steps (a) that 15ml contains 0.2g Re
2, then 120 DEG C of dryings 4 hours; The c SiO containing Re and P that () obtains with chloro-iridic acid aqueous impregnation step (b) that 15ml contains 0.2g Ir
2, then 120 DEG C of dryings 4 hours, then 500 DEG C of roastings 4 hours, obtained described catalyst.
Embodiment 7
Catalyst is Ir/Re/W/SiO
2, the weight of catalyst consists of: Ir is 2%, Re be 2%, W is 0.03%, and all the other are carrier S iO
2.
This catalyst is prepared by following step: (a) contains the ammonium metatungstate aqueous solution dipping 9.597g SiO of 0.003g W with 15ml
2, then 120 DEG C of dryings 4 hours, then 700 DEG C of roastings 4 hours; The b SiO that impregnated of W component that () obtains with rehenic acid aqueous ammonium impregnation steps (a) that 15ml contains 0.2g Re
2, then 120 DEG C of dryings 4 hours; The c SiO containing Re and W that () obtains with chloro-iridic acid aqueous impregnation step (b) that 15ml contains 0.2g Ir
2, then 120 DEG C of dryings 4 hours, then 500 DEG C of roastings 4 hours, obtained described catalyst.
Embodiment 8
Catalyst is Ir/Re/Zr/SiO
2, the weight of catalyst consists of: Ir is 2%, Re be 2%, Zr is 0.03%, and all the other are carrier S iO
2.
This catalyst is prepared by following step: (a) contains the zirconium nitrate aqueous impregnation 9.597g SiO of 0.003g Zr with 15ml
2, then 120 DEG C of dryings 4 hours, then 700 DEG C of roastings 4 hours; The b SiO that impregnated of Zr component that () obtains with rehenic acid aqueous ammonium impregnation steps (a) that 15ml contains 0.2g Re
2, then 120 DEG C of dryings 4 hours; The c SiO containing Re and Zr that () obtains with chloro-iridic acid aqueous impregnation step (b) that 15ml contains 0.2g Ir
2, then 120 DEG C of dryings 4 hours, then 500 DEG C of roastings 4 hours, obtained described catalyst.
Embodiment 9
Catalyst is Ir/Re/Mg/SiO
2, the weight of catalyst consists of: Ir is 2%, Re be 2%, Mg is 0.03%, and all the other are carrier S iO
2.
This catalyst is prepared by following step: (a) contains the magnesium nitrate aqueous solution dipping 9.597g SiO of 0.003g Mg with 15ml
2, then 120 DEG C of dryings 4 hours, then 700 DEG C of roastings 4 hours; The b SiO that impregnated of Mg component that () obtains with rehenic acid aqueous ammonium impregnation steps (a) that 15ml contains 0.2g Re
2, then 120 DEG C of dryings 4 hours; The c SiO containing Re and Mg that () obtains with chloro-iridic acid aqueous impregnation step (b) that 15ml contains 0.2g Ir
2, then 120 DEG C of dryings 4 hours, then 500 DEG C of roastings 4 hours, obtained described catalyst.
Embodiment 10
Catalyst is Ir/Re/Zn/SiO
2, the weight of catalyst consists of: Ir is 2%, Re be 2%, Zn is 0.03%, and all the other are carrier S iO
2.
This catalyst is prepared by following step: (a) contains the zinc nitrate aqueous solution dipping 9.597g SiO of 0.003g Zn with 15ml
2, then 120 DEG C of dryings 4 hours, then 700 DEG C of roastings 4 hours; The b SiO that impregnated of Zn component that () obtains with rehenic acid aqueous ammonium impregnation steps (a) that 15ml contains 0.2g Re
2, then 120 DEG C of dryings 4 hours; The c SiO containing Re and Zn that () obtains with chloro-iridic acid aqueous impregnation step (b) that 15ml contains 0.2g Ir
2, then 120 DEG C of dryings 4 hours, then 500 DEG C of roastings 4 hours, obtained described catalyst.
Embodiment 11
Catalyst is Ir/Re/HZSM-5, and the weight of catalyst consists of: Ir is 2%, Re is 2%, and all the other are carrier HZSM-5 molecular sieve (SiO
2/ Al
2o
3=50).
This catalyst is prepared by following step: (a) contains the rehenic acid aqueous ammonium dipping 9.6g HZSM-5 molecular sieve of 0.2g Re, then 120 DEG C of dryings 4 hours with 15ml; The b HZSM-5 containing Re component that () obtains with chloro-iridic acid aqueous impregnation step (a) that 15ml contains 0.2gIr, then 120 DEG C of dryings 4 hours, then 500 DEG C of roastings 4 hours, obtained described catalyst.
Comparative example 1
Catalyst is Re/Ir/SiO
2, the weight of catalyst consists of: Ir is 2%, Re is 2%, and all the other are carrier S iO
2.
This catalyst is prepared by following step: (a) contains the chloro-iridic acid rehenic acid aqueous ammonium dipping 9.6g SiO of 0.2g Ir with 15ml
2, then 120 DEG C of dryings 4 hours; The b SiO containing Ir component that () obtains with rehenic acid aqueous ammonium impregnation steps (a) that 15ml contains 0.2g Re
2, then 120 DEG C of dryings 4 hours, then 500 DEG C of roastings 4 hours, obtained described catalyst.
Comparative example 2
Catalyst is Re/Ir/SiO
2, the weight of catalyst consists of: Ir is 2%, Re is 2%, and all the other are carrier S iO
2.
This catalyst is prepared by following step: (a) contains the chloro-iridic acid rehenic acid aqueous ammonium dipping 9.6g SiO of 0.2g Ir with 15ml
2, then 120 DEG C of dryings 4 hours, then 500 DEG C of roastings 4 hours; The b SiO containing Ir component that () obtains with rehenic acid aqueous ammonium impregnation steps (a) that 15ml contains 0.2g Re
2, then 120 DEG C of dryings 4 hours, then 500 DEG C of roastings 4 hours, obtained described catalyst.
Evaluating catalyst
The evaluation of the catalyst obtained according to embodiment 1 ~ 11 and comparative example 1 and 2 is carried out respectively on continuous fixed bed reactor, and the loading amount of each catalyst is 1.5g.The liquid phase feed of hydrogenation reaction is the weight content of glycerine is the aqueous solution of 80%, sends into reactor continuously by feed pump, and the composition of the material of outflow reactor is by gas chromatographic analysis and calculate the selective of glycerol conversion yield and each product.Hydrogenation conditions is: temperature 130 DEG C, pressure 8.0MPa, liquid weight air speed 0.5h
-1, H
2/ glycerol feed molar ratio is 15.2.
Evaluating catalyst the results are shown in table 1, there is shown glycerol conversion yield and primary product selective data, and other accessory substance, if ethane etc. is due to selective very low, does not affect the explanation to catalyst of the present invention, therefore excludes table 1.
Visible by the evaluation result of embodiment 1 ~ 11 and comparative example 1,2; catalyst according to the embodiment of the present invention 1 ~ 11 is used for glycerine hydrogenation system 1; during ammediol; glycerine at certain temperature and Hydrogen Vapor Pressure condition with high activity and highly selective is converted into 1; ammediol; make directly hydrogenizing glycerol 1,3-PD process have better economy, there is better large-scale production prospect.
Table 1: the catalyst of embodiment 1 ~ 11 and comparative example 1,2 is used for preparing 1,3-propylene glycol by hydrogenation of glycerin evaluation result:
Below to invention has been detailed description, but the present invention is not limited to detailed description of the invention described herein.It will be appreciated by those skilled in the art that in the case without departing from the scope of the present invention, other changes and distortion can be made.Scope of the present invention is defined by the following claims.
Claims (10)
1. for a catalyst for preparing 1,3-propylene glycol by hydrogenation of glycerin, it is characterized in that, described catalyst is with SiO
2or HZSM-5 molecular sieve is carrier, with Re and Ir for main active component, wherein said main active component Re and Ir is carried on described carrier by infusion process simultaneously or by the order of first load Re load Ir again.
2. the catalyst for preparing 1,3-propylene glycol by hydrogenation of glycerin according to claim 1, is characterized in that, based on the gross weight of described catalyst, in described catalyst, the content of each component is: the content of Re is the content of 0.2% ~ 5.0%, Ir is 0.2% ~ 5.0%, and all the other are described carrier.
3. the catalyst for preparing 1,3-propylene glycol by hydrogenation of glycerin according to claim 1 and 2, is characterized in that, described catalyst is also containing adjuvant component.
4. the catalyst for preparing 1,3-propylene glycol by hydrogenation of glycerin according to claim 3, is characterized in that, described adjuvant component is one or more in Al, Zn, P, Mg, Zr and W.
5. according to claim 4 for glycerine hydrogenation system 1, the catalyst of ammediol, it is characterized in that, based on the gross weight of described catalyst, in described catalyst, the content of each component is: the content of Re is 0.2% ~ 5.0%, the content of Ir is 0.2% ~ 5.0%, and the content of described adjuvant component is 0.01% ~ 0.05%, and all the other are described carrier.
6. prepare according to claim 1 for glycerine hydrogenation system 1 for one kind, the method of the catalyst of ammediol, it is characterized in that, described method comprises be carried on described carrier by described main active component Re and Ir by co-impregnation simultaneously, and wherein said co-impregnation comprises: (a) is by the solution of composition preparation containing Re and Ir of described catalyst; The b SiO of solution impregnation as described carrier containing Re and Ir that () obtains by composition step (a) of described catalyst
2or HZSM-5 molecular sieve, finally carry out drying and roasting.
7. prepare according to claim 1 for glycerine hydrogenation system 1 for one kind, the method of the catalyst of ammediol, it is characterized in that, described method comprises and is carried on described carrier by described main active component Re and Ir successively by step impregnation method, and wherein said step impregnation method comprises: (a) is by solution containing Re of the composition preparation of described catalyst and with the SiO of gained solution impregnation as described carrier
2or HZSM-5 molecular sieve, then drying also carries out roasting alternatively; B (), by the composition preparation of described catalyst containing the solution of Ir, the described carrier containing Re component after the solution impregnation drying containing Ir that (c) obtains by step (b) and/or roasting, finally carries out drying also roasting.
8. one kind prepare according to any one of claim 3-5 for glycerine hydrogenation system 1, the method of the catalyst of ammediol, it is characterized in that, described adjuvant component is carried on described carrier by infusion process, wherein first by composition carrier described in the solution impregnation containing described adjuvant component of described catalyst, then drying also carries out roasting alternatively, then by main active component described in the method load according to claim 6 or 7.
9. the method according to any one of claim 6-8, is characterized in that, the temperature of described drying is 90 ~ 150 DEG C and the time is 2 ~ 15 hours, and the temperature of described roasting is 200 ~ 950 DEG C and the time is 2 ~ 10 hours.
10. the method according to any one of claim 6-8, is characterized in that, the described solution containing Re is rehenic acid aqueous ammonium; The described solution containing Ir is the chloro-iridic acid aqueous solution; The described solution containing adjuvant component is the mixture of one or more in aluminum nitrate aqueous solution, zinc nitrate aqueous solution, phosphate aqueous solution, magnesium nitrate aqueous solution, the zirconium nitrate aqueous solution, zirconyl nitrate solution and ammonium metatungstate aqueous solution.
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CN106807371A (en) * | 2015-11-30 | 2017-06-09 | 中国科学院大连化学物理研究所 | Hydrogenolysis of glycerin prepares egg-shell catalyst and its preparation and the application of 1,3- propane diols |
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CN117563593A (en) * | 2024-01-17 | 2024-02-20 | 华东理工大学 | Catalyst for producing 1, 3-propylene glycol by hydrogenolysis of glycerol and preparation method and application thereof |
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CN107159300A (en) * | 2017-06-27 | 2017-09-15 | 太原理工大学 | A kind of support type mesoporous molecular sieve catalyst and its preparation method and application |
CN109395731A (en) * | 2017-08-18 | 2019-03-01 | 中国石油化工股份有限公司 | Condensed-nuclei aromatics selective hydrocatalyst |
CN109395731B (en) * | 2017-08-18 | 2021-09-03 | 中国石油化工股份有限公司 | Polycyclic aromatic hydrocarbon selective hydrogenation catalyst |
CN109608307A (en) * | 2017-09-30 | 2019-04-12 | 张家港美景荣化学工业有限公司 | Method for preparing 1, 3-propylene glycol by glycerol hydrogenolysis and reaction system thereof |
CN109608307B (en) * | 2017-09-30 | 2022-12-20 | 张家港美景荣化学工业有限公司 | Method for preparing 1, 3-propylene glycol by glycerol hydrogenolysis and reaction system thereof |
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CN117563593B (en) * | 2024-01-17 | 2024-03-26 | 华东理工大学 | Catalyst for producing 1, 3-propylene glycol by hydrogenolysis of glycerol and preparation method and application thereof |
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