CN104275181A - Pd-Re catalyst for propylene glycol preparation by glycerol hydrogenolysis and preparation method thereof - Google Patents
Pd-Re catalyst for propylene glycol preparation by glycerol hydrogenolysis and preparation method thereof Download PDFInfo
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- CN104275181A CN104275181A CN201310286123.1A CN201310286123A CN104275181A CN 104275181 A CN104275181 A CN 104275181A CN 201310286123 A CN201310286123 A CN 201310286123A CN 104275181 A CN104275181 A CN 104275181A
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Abstract
The invention relates to a Pd-Re catalyst for propylene glycol preparation by glycerol hydrogenolysis and a preparation method thereof and belongs to the technical field of comprehensive utilization of resources and fine chemical engineering. The invention is characterized in that Pd is used as a main catalyst component, Re is used as a co-catalyst component and an inorganic oxide or carbon nanotube is used as a carrier; a supported Pd-Re catalyst precursor is prepared by an immersion method; and without roasting, hydrogen is directly used for reduction, so as to obtain the supported Pd-Re catalyst. The supported Pd-Re catalyst prepared by the method is used in a glycerol hydrogenolysis reaction so as to directly convert glycerol to propylene glycol, and has high activity and sensitivity.
Description
Technical field
The present invention relates to a kind of use without roasting only through Pd-Re catalyst prepared by the method for reduction treatment presoma, prepare the method for propane diols in the presence of the catalyst from glycerine direct hydrogenation, belong to field of fine chemical.
Background technology
As a kind of novel energy, biodiesel, with its environmental friendliness, the various advantage such as renewable, obtains both domestic and external greatly developing.Use plant or animal fat, carrying out ester exchange reaction with methyl alcohol or ethanol can obtain biodiesel, but accessory substance glycerine also generates simultaneously.The average biodiesel often generating 9Kg, i.e. the glycerine of by-product 1Kg.And in traditional application, glycerine can be used for national defense industry (as produced trinitin etc.), field of medicaments (as produced nitroglycerine), skin care item industry (as NMF etc.), food industry (as produced sweetener etc.).But the glycerine that the glycerine that these traditional applications consume produces well below production of biodiesel process.Therefore, research and develop technology glycerine being converted into high additive value downstream product, significant to comprehensive utilization biomass resource.
It is one of glycerine trans-utilization approach that hydrogenolysis of glycyl alcohol prepares propane diols.The propane diols produced comprises, 1,3-PD and 1,2-PD.1,3-PD is a kind of important industrial chemicals and medicine intermediate.1,3-PD can have the New Material PTT of softness, fluffy and favorable elasticity with Production of Terephthalic Acid.1,2-PD is also a kind of widely used industrial chemicals.May be used for producing unsaturated polyester resin; Cosmetic industry is applied to as wetting agent; Also antifreezing agent etc. can be used as.
Traditional 1,3-PD industrial production process has, German Degussa house journal (EP412 337,1991) technology, uses methacrylaldehyde, prepares under the catalytic hydrogenation of phosphate cpd and Raney's nickel; Shell house journal of the U.S. (US5356 827,1993 and US5 777 182,1998) technology, uses oxirane, prepares under the catalytic hydrogenation of carbonyl cobalt and Raney nickel.But the production method of the 1,3-PD of these patent reports, complex process, productive rate is lower, and the raw material used is non-renewable resource, thus makes the expensive of 1,3-PD.If utilize the glycerine of biomass source directly to generate propane diols, so both can reduce biodiesel cost, the price of propane diols can be reduced again.
Chinese patent (CNIO1381280A) reports a kind of method of hydrogenolysis of glycyl alcohol propane diols, the method working load type Ni catalyst, be obtained by reacting higher glycerine conversion ratio at 200 DEG C and 1,2-PD selective.But do not have 1,3-PD to generate.Document (Green Chem., 2009,11,1511-1513) reports with Pd/Fe
2o
3as catalyst, 2-propyl alcohol as solvent and hydrogen source, at 180 DEG C, under the inert gas pressure of 5bar, the method of the hydrogen utilizing the dehydrogenation of 2-propyl alcohol to produce and glycerine reaction, obtains the selective of high glycerine conversion ratio and 1,2-PD, but the method uses 2-propyl alcohol to be solvent, and the large usage quantity of Metal Palladium, and 1,3-PD is not had to generate.Another document (Journal of Catalysis, 2012,296,1) discloses with Cu
0.4/ Zn
5.6-xmg
xal
2o
8.6carry out the method for hydrogenolysis of glycyl alcohol reaction as catalyst, at 200 DEG C, obtain high glycerine conversion ratio and 1,2-PD selective, but there is no the generation of 1,3-PD.Document (Green Chem., 2011,13,2004) reports and uses Pt/SO4
2-/ ZrO
2as catalyst, with DMI (1,3-dimethyl-2-imidazolinone) method of hydrogenolysis of glycyl alcohol is carried out as solvent, higher glycerine conversion ratio and 1 can be obtained, ammediol productive rate, but the DMI solvent price that the method uses costly and have toxicity, in addition, DMI meeting itself and glycerine generation hydrogenolysis.Although existing technology can be converted into 1 hydrogenolysis of glycyl alcohol under certain conditions, 2-propane diols, but the catalyst that some technology complex process, technology of having on catalyst preparing use expensive poisonous reagent, the technology that has uses still can not be converted into 1,3-PD glycerine.
Summary of the invention
The object of this invention is to provide a kind of Pd-Re bicomponent catalyst of preparation technology's simple and effective, directly prepare propane diols from glycerine.Catalyst provided by the invention and directly prepared the method for propane diols by glycerine, it is characterized in that: described method adopts loading type Pd-Re bicomponent catalyst, this catalyst precursor is without roasting, the only process of experience hydrogen reducing, with glycerine and hydrogen for raw material, under relatively mild condition, prepare propane diols.
The operating procedure of the preparation method of loading type Pd-Re bicomponent catalyst involved in the present invention and hydrogenolysis of glycyl alcohol reaction is as follows:
1, the preparation of loading type Pd-Re catalyst
By a certain amount of 0.1mol/L palladium bichloride (PdCl
2) hydrochloric acid solution and a certain amount of 0.1mol/L perrhenic acid (HReO
4) after aqueous solution, add a certain amount of carrier, evaporating water after dipping certain hour under stirring at normal temperatures, then pressed powder is placed in 110 DEG C of baking ovens dry 12 hours, the Pd-Re catalyst precursor obtained at 250 DEG C of reductase 12s hour, obtains loading type Pd-Re bicomponent catalyst in pure hydrogen.
2, hydrogenolysis of glycyl alcohol reaction operation
(1) in autoclave, a certain amount of Pd-Re catalyst is added and mass fraction is the glycerin solution of 40%;
(2) reactor is airtight and after leak test, uses the residual air in hydrogen exchange reactor, reactor is placed on heating furnace and heats;
(3), after arriving reaction temperature, in reactor, hydrogen is filled with to reaction pressure;
(4) under agitation react.After reaction terminates, take out reactor, be cooled to below room temperature, by reactor pressure release, after opening kettle cover, add a certain amount of internal standard compound matter (diethylene glycol dimethyl ether and 1,4-butanediol), after mixing, liquid-solid mixture is taken out and carry out centrifugation, the liquid gas-chromatography obtained is analyzed, and calculates conversion ratio and products collection efficiency.
Method provided by the invention, catalyst preparation process is simple, and presoma only experiences hydrogen reducing Pd-Re catalyst without roasting has higher activity.
Detailed description of the invention
Below by embodiment, the present invention is described further.
Embodiment 1
(1) preparation of 5%Pd-5%Re/SBA-15 presoma
By 4.00g blocked copolymer p 123 (commercially available reagent: (PEO)
20(PPOX)
70(PEO)
20) be dissolved in the hydrochloric acid solution of the 2mol/L of 122mL, at 35 DEG C after stirring and dissolving, add ethyl orthosilicate (commercially available reagent) 9.5mL that mass fraction is 28%, stirring is continued after 20 hours at 35 DEG C, be warming up to 80 DEG C and leave standstill aging 24 hours in 80 DEG C, the gel obtained is spent deionized water cyclic washing to filtrate in neutral, the gel finally obtained at 40 DEG C dry 48 hours, then 500 DEG C of roastings 6 hours, carrier solids powder mesoporous silicon oxide (SBA-15) is obtained.
By the PdCl of 0.1mol/L
2the HReO of (commercially available reagent) hydrochloric acid solution 5.2mL and 0.1mol/L
4(commercially available reagent) aqueous solution 3.0mL mixes, and stirs, and then above-mentioned SBA-15 carrier 1.00g is added in this mixed liquor, at room temperature stir dipping after 10 hours, evaporating water, then in 110 DEG C of baking ovens dry 12 hours, obtains catalyst precursor.The metal loading of Pd and Re is respectively 5% (mass percent).
(2) activation process of 5%Pd-5%Re/SBA-15 presoma
Presoma 0.20g above-mentioned steps prepared is placed in glass tube, passes into hydrogen, and reductase 12 hour at 250 DEG C obtains 5%Pd-5%Re/SBA-15 catalyst, is labeled as 5Pd-5Re/SBA-15.
(3), hydrogenolysis of glycyl alcohol reaction and product analysis on 5Pd-5Re/SBA-15 catalyst
In the autoclave of 100mL, add the glycerin solution 10mL of the above-mentioned 5Pd-5Re/SBA-15 catalyst of 0.15g and 40% mass fraction, after reactor is airtight, be placed in ice-water bath, be filled with the residual air in 2MPa hydrogen exchange reactor, in triplicate, reactor be placed on heating furnace and carry out being heated to reaction temperature 200 DEG C, 8MPa hydrogen is filled with, stirring reaction 18 hours under the rotating speed of 700rpm in reactor.After reaction terminates, from heating furnace, take out reactor, be cooled to below room temperature, Pressure Drop in still to normal pressure, open kettle cover, add internal standard compound matter (diethylene glycol dimethyl ether and BDO), mix, liquid-solid mixture is taken out and carries out centrifugation, the liquid gas-chromatography obtained is analyzed, and calculates glycerine conversion ratio, 1, the productive rate of 2-propane diols and 1,3-PD and the productive rate of propyl alcohol.Reaction result lists in table 1.
Embodiment 2
(1), the preparation of 5%Pd-10%Re/SBA-15 presoma
Except the HReO of 0.1mol/L
4aqueous solution use amount is outside 6.3mL, and other step is with the step (1) of embodiment 1.
(2), the activation process of 5%Pd-10%Re/SBA-15 presoma
Except using the presoma of 5%Pd-10%Re/SBA-15, other step is with the step (2) of embodiment 1.Obtain 5%Pd-10%Re/SBA-15 catalyst, be labeled as 5Pd-10Re/SBA-15.
(3), hydrogenolysis of glycyl alcohol reaction and product analysis on 5Pd-10Re/SBA-15 catalyst
Except using 5Pd-10Re/SBA-15 catalyst, other step is with the step (3) of embodiment 1, and reaction result lists in table 1.
Embodiment 3
(1), 5%Pd-5%Re/A1
2o
3the preparation of presoma
Except using carrier A 1
2o
3(commercially available reagent) replaces outside SBA-15, and other step is with the step (1) of embodiment 1.
(2), 5%Pd-5%Re/Al
2o
3the activation process of presoma
Except using 5%Pd-5%Re/Al
2o
3presoma outside, other step is with the step (2) of embodiment 1.Obtain 5%Pd-5%Re/Al
2o
3catalyst, is labeled as 5Pd-5Re/Al
2o
3.
(3), 5Pd-5Re/Al
2o
3hydrogenolysis of glycyl alcohol reaction and product analysis on catalyst
Except using 5Pd-5Re/Al
2o
3outside catalyst, other step is with the step (3) of embodiment 1, and reaction result lists in table 1.
Embodiment 4
(1), 5%Pd-5%Re/TiO
2the preparation of presoma
Except using carrier TiO
2(commercially available reagent) replaces outside SBA-15, and other step is with the step (1) of embodiment 1.
(2), 5%Pd-5%Re/TiO
2the activation process of presoma
Except using 5%Pd-5%Re/TiO
2presoma outside, other step is with the step (2) of embodiment 1.Obtain 5%Pd-5%Re/TiO
2catalyst, is labeled as 5Pd-5Re/TiO
2.
(3), 5Pd-5Re/TiO
2hydrogenolysis of glycyl alcohol reaction and product analysis on catalyst
Except using 5Pd-5Re/TiO
2outside catalyst, other step is with the step (3) of embodiment 1, and reaction result lists in table 1.
Embodiment 5
(1), the preparation of 5%Pd-5%Re/MgO presoma
Except using carrier MgO (commercially available reagent) and replacing SBA-15, other step is with the step (1) of embodiment 1.
(2), the activation process of 5%Pd-5%Re/MgO presoma
Except using the presoma of 5%Pd-5%Re/MgO, other step is with the step (2) of embodiment 1.Obtain 5%Pd-5%Re/MgO catalyst, be labeled as 5Pd-5Re/MgO.
(3), hydrogenolysis of glycyl alcohol reaction and product analysis on 5Pd-5Re/MgO catalyst
Except using 5Pd-5Re/MgO catalyst, other step is with the step (3) of embodiment 1, and reaction result lists in table 1.
Embodiment 6
(1), 5%Pd-5%Re/La
2o
3the preparation of presoma
0.01mol nitric hydrate lanthanum (commercially available reagent) and 1g softex kw (commercially available reagent) are dissolved in 40ml deionized water, under agitation the 20ml sodium hydroxide solution (1mol/L) configured dropwise is instilled in lanthanum nitrate hexahydrate, form white precipitate.Above-mentioned white precipitate is continued stirring 6 hours at 70 DEG C.Then with the concentrated ammonia liquor of 25%, pH value is adjusted to 10, and moves in 100ml water heating kettle, hydro-thermal 48 hours at 100 DEG C.By the liquid-solid mixture deionized water that obtains after hydro-thermal and ethanol cyclic washing, then 110 DEG C of oven dry.By the roasting 3 hours at 700 DEG C of above-mentioned solid, obtain carrier La
2o
3.
Except using carrier La
2o
3replace outside SBA-15, other step is with the step (1) of embodiment 1.
(2), 5%Pd-5%Re/La
2o
3the activation process of presoma
Except using 5%Pd-5%Re/La
2o
3presoma outside, other step is with the step (2) of embodiment 1.Obtain 5%Pd-5%Re/La
2o
3catalyst, is labeled as 5Pd-5Re/La
2o
3.
(3), 5Pd-5Re/La
2o
3hydrogenolysis of glycyl alcohol reaction and product analysis on catalyst
Except using 5Pd-5Re/La
2o
3outside catalyst, other step is with the step (3) of embodiment 1, and reaction result lists in table 1.
Embodiment 7
(1), the preparation of 5%Pd-5%Re/CNTs presoma
Except using support C NTs (commercially available reagent) and replacing SBA-15, other step is with the step (1) of embodiment 1.
(2), the activation process of 5%Pd-5%Re/CNTs presoma
Except using the presoma of 5%Pd-5%Re/CNTs, other step is with the step (2) of embodiment 1.Obtain 5%Pd-5%Re/CNTs catalyst, be labeled as 5Pd-5Re/CNTs.
(3), hydrogenolysis of glycyl alcohol reaction and product analysis on 5Pd-5Re/CNTs catalyst
Except using 5Pd-5Re/CNTs catalyst, other step is with the step (3) of embodiment 1, and reaction result lists in table 1.
Comparative example 1
(1), the preparation of 5%Pd/SBA-15 catalyst precursor
Except in catalyst preparing, only use the PdCl of 0.1mol/L
2hydrochloric acid solution 5.2mL and do not use HReO
4outside the aqueous solution, other step is with the step (1) of embodiment 1.
(2), the activation process of 5%Pd/SBA-15 catalyst precursor
Except using the presoma of 5%Pd/SBA-15, other step, with the step (2) of embodiment 1, is labeled as 5Pd/SBA-15.
(3), hydrogenolysis of glycyl alcohol reaction and product analysis on 5Pd/SBA-15 catalyst
Except using 5Pd/SBA-15 catalyst, other step is with the step (3) of embodiment 1, and reaction result lists in table 1.
Comparative example 2
(1), 5%Pd/Al
2o
3the preparation of catalyst precursor
Except in catalyst preparing, only use the PdCl of 0.1mol/L
2hydrochloric acid solution 5.2mL and do not use HReO
4outside the aqueous solution, other step is with the step (1) of embodiment 3.
(2), 5%Pd/Al
2o
3the activation process of catalyst precursor
Except using 5%Pd/Al
2o
3presoma outside, other step, with the step (2) of embodiment 3, is labeled as 5Pd/Al
2o
3.
(3), 5Pd/Al
2o
3hydrogenolysis of glycyl alcohol reaction and product analysis on catalyst
Except using 5Pd/Al
2o
3outside catalyst, other step is with the step (3) of embodiment 3, and reaction result lists in table 1.
Comparative example 3
(1), 5%Pd/TiO
2the preparation of catalyst precursor
Except in catalyst preparing, only use the PdCl of 0.1mol/L
2hydrochloric acid solution 5.2mL and do not use HReO
4outside the aqueous solution, other step is with the step (1) of embodiment 4.
(2), 5%Pd/TiO
2the activation process of catalyst precursor
Except using 5%Pd/TiO
2presoma outside, other step, with the step (2) of embodiment 4, is labeled as 5Pd/TiO
2.
(3), 5Pd/TiO
2hydrogenolysis of glycyl alcohol reaction and product analysis on catalyst
Except using 5Pd/TiO
2outside catalyst, other step is with the step (3) of embodiment 4, and reaction result lists in table 1.
Comparative example 4
(1), the preparation of 5%Pd/MgO catalyst precursor
Except in catalyst preparing, only use the PdCl of 0.1mol/L
2hydrochloric acid solution 5.2mL and do not use HReO
4outside the aqueous solution, other step is with the step (1) of embodiment 5.
(2), the activation process of 5%Pd/MgO catalyst precursor
Except using the presoma of 5%Pd/MgO, other step, with the step (2) of embodiment 5, is labeled as 5Pd/MgO.
(3), hydrogenolysis of glycyl alcohol reaction and product analysis on 5Pd/MgO catalyst
Except using 5Pd/MgO catalyst, other step is with the step (3) of embodiment 5, and reaction result lists in table 1.
Comparative example 5
(1), 5%Pd/La
2o
3the preparation of catalyst precursor
Except in catalyst preparing, only use the PdCl of 0.1mol/L
2hydrochloric acid solution 5.2mL and do not use HReO
4outside the aqueous solution, other step is with the step (1) of embodiment 6.
(2), 5%Pd/La
2o
3the activation process of catalyst precursor
Except using 5%Pd/La
2o
3presoma outside, other step, with the step (2) of embodiment 6, is labeled as 5Pd/La
2o
3.
(3), 5Pd/La
2o
3hydrogenolysis of glycyl alcohol reaction and product analysis on catalyst
Except using 5Pd/La
2o
3outside catalyst, other step is with the step (3) of embodiment 6, and reaction result lists in table 1.
Comparative example 6
(1), the preparation of 5%Pd/CNTs catalyst precursor
Except in catalyst preparing, only use the PdCl of 0.1mol/L
2hydrochloric acid solution 5.2mL and do not use HReO
4outside the aqueous solution, other step is with the step (1) of embodiment 7.
(2), the activation process of 5%Pd/CNTs catalyst precursor
Except using the presoma of 5%Pd/CNTs, other step, with the step (2) of embodiment 7, is labeled as 5Pd/CNTs.
(3), hydrogenolysis of glycyl alcohol reaction and product analysis on 5Pd/CNTs catalyst
Except using 5Pd/CNTs catalyst, other step is with the step (3) of embodiment 7, and reaction result lists in table 1.
Comparative example 7
(1), the preparation of 5%Pd-5%Re/SBA-15-AR catalyst precursor
5%Pd-5%Re/SBA-15-AR precursor power step is with the step (1) of embodiment 1.
(2), the activation process of 5%Pd-5%Re/SBA-15-AR catalyst precursor
The obtained presoma of above-mentioned steps (1) before hydrogen reducing first in Muffle furnace in atmosphere in 350 DEG C of roastings 2 hours, other step is with the step (2) of embodiment 1, obtain 5%Pd-5%Re/SBA-15-AR catalyst, be labeled as 5Pd-5Re/SBA-15-AR.
(3), hydrogenolysis of glycyl alcohol reaction and product analysis on 5Pd-5Re/SBA-15-AR catalyst
Except using 5Pd-5Re/SBA-15-AR catalyst and replacing 5Pd-5Re/SBA-15 catalyst, other step is with the step (3) of embodiment 1, and reaction result lists in table 1.
Comparative example 8
(1), the preparation of 5%Pd-1%Re/SBA-15 catalyst precursor
Except the HReO of 0.1mol/L
4aqueous solution use amount is outside 0.6mL, and other step is with the step (1) of embodiment 1.
(2), the activation process of 5%Pd-1%Re/SBA-15 catalyst precursor
Except using the presoma of 5%Pd-1%Re/SBA-15, other step is with the step (2) of embodiment 1.Obtain 5%Pd-1%Re/SBA-15 catalyst, be labeled as 5Pd-1Re/SBA-15.
(3), hydrogenolysis of glycyl alcohol reaction and product analysis on 5Pd-1Re/SBA-15 catalyst
Except using 5Pd-1Re/SBA-15 catalyst, other step is with the step (3) of embodiment 1, and reaction result lists in table 1.
Table 1
Note: a: dried catalyst precursor is reductase 12 hour in 250 DEG C of current downflow hydrogen directly.
B: dried catalyst precursor is roasting 2 hours in still air, then reductase 12 hour in 250 DEG C of current downflow hydrogen at 350 DEG C first.
Claims (10)
1. the Pd-Re Catalysts and its preparation method for hydrogenolysis of glycyl alcohol propane diols, it is characterized in that: take Pd as main catalyst component, Re is co-catalyst component, inorganic oxide or CNT be carrier, infusion process is adopted to prepare loading type Pd-Re catalyst precursor, this presoma only through hydrogen reducing process, obtains loading type Pd-Re catalyst without roasting.Use loading type Pd-Re catalyst provided by the invention to carry out hydrogenolysis of glycyl alcohol reaction, glycerine can be converted into propane diols.Its preparation process is:
(1) use infusion process to prepare loading type Pd-Re catalyst, carrier immersed the aqueous solution of Pd inorganic salts and Re inorganic salts, dried catalyst precursor without roasting, directly reduce in hydrogen after for reaction;
(2) in autoclave, a certain amount of loading type Pd-Re catalyst and glycerin solution is added;
(3) reactor airtight after, use the air in hydrogen exchange reactor, reactor be placed on heating furnace and heat;
(4), after arriving reaction temperature, in reactor, hydrogen is filled with to reaction pressure;
(5) under agitation react, reactor is taken out after end, be cooled to below room temperature, kettle cover is opened by after reactor pressure release, add internal standard compound matter to mix, liquid-solid mixture is taken out and carries out centrifugation, the liquid gas-chromatography obtained is carried out analyzing and calculates conversion ratio and products collection efficiency.
2. in accordance with the method for claim 1, it is characterized in that: described loading type Pd-Re catalyst, its dried presoma only experiences hydrogen reducing process without calcination process.
3. in accordance with the method for claim 1, it is characterized in that: described Pd inorganic salts are palladium bichloride (PdCl
2), Re inorganic salts are perrhenic acid (HReO
4).
4. in accordance with the method for claim 1, it is characterized in that: described inorganic oxide is ordered meso-porous silicon oxide (SBA-15), aluminium oxide (Al
2o
3), titanium oxide (TiO
2), magnesia (MgO) and lanthana (La
2o
3), described CNT is multi-walled carbon nano-tubes (CNTs).
5. in accordance with the method for claim 1, it is characterized in that: described propane diols is 1,2-PD and 1,3-PD.
6. in accordance with the method for claim 1, it is characterized in that: in described hydrogenolysis of glycyl alcohol reaction, the consumption of loading type Pd-Re catalyst is: the mass ratio of metal Pd and glycerine is 1/585.
7. in accordance with the method for claim 1, it is characterized in that: in described loading type Pd-Re catalyst, the mass fraction of metal Pd is 5%, and the mass fraction of metal Re is 5% ~ 10%.
8. in accordance with the method for claim 1, it is characterized in that: the reaction temperature in (4) of described step 1 is 200 DEG C.
9. in accordance with the method for claim 1, it is characterized in that: the pressure of the hydrogen in (4) of described step 1 is 8MPa.
10. in accordance with the method for claim 1, it is characterized in that: in (5) of described step 1, react and carry out with batch (-type), 18 hours reaction time.
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| CN108654610A (en) * | 2017-03-28 | 2018-10-16 | 中国石油化工股份有限公司 | The preparation method and catalyst and cycloalkane hydrogenolysis open-loop method of a kind of noble metal carrier catalyst |
| CN108654609A (en) * | 2017-03-28 | 2018-10-16 | 中国石油化工股份有限公司 | A kind of platiniferous and or supported palladium catalyst preparation method and catalyst and hydrogenolysis of glycerin method |
| CN108654610B (en) * | 2017-03-28 | 2022-08-09 | 中国石油化工股份有限公司 | Preparation method of noble metal supported catalyst, catalyst and naphthenic hydrocarbon hydrogenolysis ring-opening method |
| CN112169795A (en) * | 2019-07-02 | 2021-01-05 | 中国科学院大连化学物理研究所 | Optimized polyol hydrogenolysis catalyst activation process |
| CN112169795B (en) * | 2019-07-02 | 2022-05-06 | 中国科学院大连化学物理研究所 | Optimized polyol hydrogenolysis catalyst activation process |
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