CN107913722B - Metal/solid acid catalyst for preparing 1, 3-propylene glycol by glycerol hydrogenation - Google Patents
Metal/solid acid catalyst for preparing 1, 3-propylene glycol by glycerol hydrogenation Download PDFInfo
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- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 title claims abstract description 115
- 239000003054 catalyst Substances 0.000 title claims abstract description 99
- 239000011973 solid acid Substances 0.000 title claims abstract description 80
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 62
- 239000002184 metal Substances 0.000 title claims abstract description 62
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 22
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims abstract description 40
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 24
- 239000010439 graphite Substances 0.000 claims abstract description 24
- 239000003607 modifier Substances 0.000 claims abstract description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 42
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims description 25
- 229940035437 1,3-propanediol Drugs 0.000 claims description 25
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 23
- 239000002131 composite material Substances 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 10
- 238000012986 modification Methods 0.000 claims description 10
- 230000004048 modification Effects 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 10
- 229920000877 Melamine resin Polymers 0.000 claims description 9
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 claims description 9
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 9
- OJYBUGUSFDKJEX-UHFFFAOYSA-N tungsten zirconium Chemical compound [Zr].[W].[W] OJYBUGUSFDKJEX-UHFFFAOYSA-N 0.000 claims description 9
- 229910052697 platinum Inorganic materials 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 6
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 claims description 5
- UTSDGYKWHMMTDM-UHFFFAOYSA-N alumane;tungsten Chemical compound [AlH3].[W] UTSDGYKWHMMTDM-UHFFFAOYSA-N 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 4
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 4
- 238000011065 in-situ storage Methods 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 2
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 2
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 2
- 238000010952 in-situ formation Methods 0.000 claims 1
- 239000007864 aqueous solution Substances 0.000 abstract description 9
- 230000007774 longterm Effects 0.000 abstract description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 49
- 235000011187 glycerol Nutrition 0.000 description 32
- 238000006243 chemical reaction Methods 0.000 description 17
- 238000002360 preparation method Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 9
- 238000012360 testing method Methods 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 229910052593 corundum Inorganic materials 0.000 description 5
- -1 polyethylene terephthalate Polymers 0.000 description 5
- 229910001845 yogo sapphire Inorganic materials 0.000 description 5
- 239000000835 fiber Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000000382 dechlorinating effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- NMYFVWYGKGVPIW-UHFFFAOYSA-N 3,7-dioxabicyclo[7.2.2]trideca-1(11),9,12-triene-2,8-dione Chemical compound O=C1OCCCOC(=O)C2=CC=C1C=C2 NMYFVWYGKGVPIW-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 241000764238 Isis Species 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007798 antifreeze agent Substances 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000012431 aqueous reaction media Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 1
- 238000007327 hydrogenolysis reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 150000003657 tungsten Chemical class 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0207—Pretreatment of the support
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/60—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by elimination of -OH groups, e.g. by dehydration
Abstract
The invention provides a metal/solid acid catalyst for preparing 1, 3-propylene glycol by glycerol hydrogenation, wherein the metal/solid acid catalyst contains a solid acid surface modifier graphite phase carbon nitride, and the content of the graphite phase carbon nitride in the metal/solid acid catalyst is 0.01-3 wt%. The metal/solid acid catalyst provided by the invention can be kept stable in an aqueous solution medium; when the catalyst is used for preparing 1, 3-propylene glycol, the catalyst has good stability in long-term operation in aqueous solution.
Description
Technical Field
The invention belongs to the technical field of chemical industry, and particularly relates to a metal/solid acid catalyst for preparing 1, 3-propylene glycol by glycerol hydrogenation.
Background
The 1, 3-propylene glycol is an important raw material in the field of fine chemical engineering, can be used for printing ink, printing and dyeing, medicaments, lubricants and antifreeze agents, and can also be used as dihydric alcohol for synthesizing heterocycles, medicament intermediates and the like. Currently, the most important use of 1, 3-propanediol is as a polymer monomer to synthesize degradable Polyester Trimethylene Terephthalate (PTT). The PTT has high-strength stability of PET (polyethylene terephthalate) and excellent forming processing type of PBT (polybutylene terephthalate); and is comparable to PA6 and PA66 in terms of elastic recovery, and exhibits soft and excellent drapability, good quality touch, and comfortable elasticity. Further, PTT also has good stain resistance and abrasion resistance. PTT has already had certain application in fields such as fibers, low-carbon materials and engineering plastics, and the potential market is huge. Taking the textile field as an example, because the PTT fiber has particularly excellent softness and elastic resilience, excellent wrinkle resistance and dimensional stability, good weather resistance and dyeing property, and good barrier property, and can withstand the disinfection of gamma rays, the clothing made by the PTT fiber fabric is comfortable to wear, soft to touch, easy to wash, quick to dry, easy to iron, and thus, the PTT fiber fabric has great market potential. Under the promotion of great demand for PTT in the industrial field, 1, 3-propanediol is certainly developed as a raw material for synthesizing PTT. At present, the main reason for limiting the large-scale application of PTT is the price of 1, 3-propanediol, so that the development of a low-cost 1, 3-propanediol synthesis process is of great significance.
At present, the hydrogenation preparation of 1, 3-propylene glycol by using glycerol as a raw material is considered to be a process route with a great development prospect. The process generally uses a metal/solid acid bifunctional catalyst and adopts an aqueous solution medium for reaction, but the process also has obvious defects that the catalyst is easy to deactivate and has poor stability, no good solution is available at present, and the process is still an important factor for preventing the process from developing to industrial application.
Disclosure of Invention
In order to solve the problems, the invention aims to provide a metal/solid acid catalyst for preparing 1, 3-propylene glycol by hydrogenating glycerol.
It is another object of the present invention to provide a method for preparing the above metal/solid acid catalyst.
In order to achieve the above object, the present invention provides a metal/solid acid catalyst for preparing 1, 3-propanediol by hydrogenation of glycerol, wherein the metal/solid acid catalyst contains graphite-phase carbon nitride as a solid acid surface modifier, and the content of the graphite-phase carbon nitride in the metal/solid acid catalyst is 0.01 wt% to 3 wt%.
In a conventional reaction system for preparing 1, 3-propanediol by hydrogenolysis of glycerol, the problem of poor stability of the used metal/solid acid catalyst generally exists, the activity of the catalyst is obviously reduced along with the progress of the reaction, and the activity of the catalyst is greatly reduced when the catalyst is operated for a short time. The applicant researches and discovers that the reason why the catalyst is easy to deactivate in the reaction system is mainly two aspects: on one hand, because an oxide/water system is in a thermodynamically metastable state, under the hydrothermal condition, the oxide is contacted with water, the rehydration of the oxide occurs, and the oxide is easily converted into a surface oxyhydroxide or hydroxide phase; on the other hand, because the oxides in the catalyst have a plurality of crystal phase structures, and the performances of the oxides in different crystal phase structures are different, when the oxides are used as the catalyst, the performances of certain specific crystal phase structures are generally required to be adopted, but the oxides are easy to generate phase change under a hydrothermal environment; both of these conditions can affect the performance of specific properties of the solid acid-containing system, resulting in the metal/solid acid catalyst being susceptible to deactivation in the system. Therefore, according to the scheme provided by the invention, the surface of the solid acid is modified by adopting a proper amount of graphite-phase carbon nitride, so that the protective modification of sites which are easy to generate rehydration or phase change on the surface of the solid acid is realized, and the stability of the metal/solid acid catalyst in an aqueous reaction medium is obviously improved.
In the above metal/solid acid catalyst for producing 1, 3-propanediol by hydrogenation of glycerin, it is not limited that only carbon nitride of graphite phase is present in the catalyst, and a small amount of carbon nitride of other phase is sometimes unavoidable. Further, the content of carbon nitride in the graphite phase is preferably limited. In general, at levels exceeding 3 wt%, the initial activity of the catalyst is greatly affected, substantially offsetting the benefits of increased stability. In a preferred embodiment provided by the present invention, the graphite phase carbon nitride is present in the metal/solid acid catalyst in an amount of from 0.05 wt% to 2 wt%; preferably 0.1 wt% to 1 wt%. In addition, the graphite phase carbon nitride can also be a graphite phase carbon nitride material which is doped or modified conventionally.
In the above-mentioned metal/solid acid catalyst for the hydrogenation of glycerol to 1, 3-propanediol, it is preferable that the active metal isIs platinum; the solid acid being ZrO2、WO3And Al2O3Preferably a tungsten aluminum composite oxide or a tungsten zirconium composite oxide.
In the above metal/solid acid catalyst for the preparation of 1, 3-propanediol by hydrogenation of glycerol, the content of active metal is preferably 0.5 to 3% by weight. In a preferred embodiment of the present invention (catalyst is described as: Pt/C)3N4@WO3/ZrO2(or Al)2O3) Platinum is used as active metal, and tungsten-aluminum composite oxide or tungsten-zirconium composite oxide is used as solid acid; wherein, the content of platinum is 1 wt% -2 wt%, the content of graphite phase carbon nitride is 0.5 wt% -1 wt%, the content of tungsten oxide is 10 wt% -15 wt%, and the rest is zirconium oxide or aluminum oxide.
The invention also provides a preparation method of the metal/solid acid catalyst, wherein in the preparation process of the catalyst, the surface modification is carried out on the solid acid in a mode of in-situ growth of graphite-phase carbon nitride, and then the loading of active metal is carried out.
In the above-mentioned method for preparing a metal/solid acid catalyst, when preparing a solid acid and supporting an active metal, a method and conditions which are conventional in the art may be employed. Mainly adds a step of graphite phase carbon nitride modification to the solid acid in the preparation process.
In the above method for preparing a metal/solid acid catalyst, preferably, the step of surface-modifying the solid acid in a manner of in-situ growing graphite-phase carbon nitride comprises:
firstly, mixing the solid acid with the raw material for preparing the graphite-phase carbon nitride, and then roasting to generate the graphite-phase carbon nitride on the surface of the solid acid, thereby realizing the surface modification of the solid acid. In a preferred embodiment of the present invention, the mixing is performed by grinding and mixing. In addition, the method can select the conventional raw materials (comprising a carbon nitrogen source and an auxiliary reagent) for preparing the graphite phase carbon nitride by a heating method in the field and the necessary conditions for generating the graphite phase carbon nitride. In a preferred embodiment of the present invention, the carbon-nitrogen source is a mixture of melamine and trichloro-s-triazine, or dicyandiamide. Further preferably, the mixture has a molar ratio of melamine to trichloro-s-triazine (1-4): 1; preferably 2: 1.
In the above method for preparing a metal/solid acid catalyst, preferably, the method further comprises a step of tabletting the mixed material before the calcination treatment.
In the above method for producing a metal/solid acid catalyst, preferably, the conditions of the calcination treatment are: keeping the temperature at 500-650 ℃ for 2-6 hours.
In a preferred embodiment of the present invention, the step of preparing the metal/solid acid catalyst comprises:
step 1, preparing a solid acid part of a catalyst;
step 2, weighing the measured solid acid obtained in the step 1 and raw materials (such as carbon nitrogen source) for preparing graphite phase carbon nitride, fully grinding and mixing, tabletting and forming, roasting the obtained sample, and cooling to room temperature to obtain graphite phase carbon nitride modified solid acid;
and 3, carrying out active metal loading on the graphite-phase carbon nitride modified solid acid prepared in the step 2 to prepare the metal/solid acid catalyst.
In one embodiment of the present invention, Pt/C is prepared3N4@WO3/ZrO2(or Al)2O3) The process comprises the following steps:
step 1, weighing the measured ZrO2(or Al)2O3) Adding required amount of tungsten salt aqueous solution, kneading for 2-5h at 50-80 ℃, drying at 100-130 ℃, and then roasting for 3-5h at 600-800 ℃ to obtain the tungsten-containing composite oxide WO3/ZrO2(or Al)2O3)；
Step 2, respectively weighing and metering the WO prepared in the step 13/ZrO2(or Al)2O3) Melamine (C)3N6H6) And trichloro-s-triazine (C)3N3Cl3) Wherein melamine (C)3N6H6) And IIIChlorotriazine (C)3N3Cl3) The molar ratio of (1-4) to (1), fully grinding and mixing, tabletting and forming, placing the obtained sample in a tube furnace, introducing high-purity nitrogen, heating to 500-700 ℃, keeping the temperature for a period of time, and cooling to room temperature to obtain C3N4@WO3/ZrO2(or Al)2O3) A sample;
step 3, measuring H with certain concentration2PtCl6Aqueous solution, weighing and metering C prepared in step 23N4@WO3/ZrO2(or Al)2O3) Soaking in the solution, standing for a period of time, oven drying, and dechlorinating to obtain Pt/C3N4@WO3/ZrO2(or Al)2O3) A catalyst. The raw materials of the step 1, the step 2 and the step 3 are used in an amount meeting the requirement of WO3: 10-15 wt%; graphite phase carbon nitride (C)3N4): 0.05-1 wt%; pt: 1-2 wt%, the rest is the requirement of carrier zirconium dioxide (or aluminum oxide).
Compared with the prior art, the scheme provided by the invention has the advantages that: the metal/solid acid catalyst containing graphite-phase carbon nitride provided by the invention can be kept stable in an aqueous medium; when the catalyst is used for preparing 1, 3-propylene glycol, the catalyst has good stability in long-term operation in aqueous solution.
Detailed Description
The technical solutions of the present invention will be described in detail below in order to clearly understand the technical features, objects, and advantages of the present invention, but the present invention is not limited to the practical scope of the present invention.
Example 1
This example provides a metal/solid acid catalyst (Pt/C)3N4@WO3/ZrO2) The preparation process comprises the following steps:
step 1, weighing and adding metered zirconium dioxide into ammonium metatungstate aqueous solution with required amount, kneading for 3 hours at 60 ℃, drying at 110 ℃, and roasting for 3 hours in air atmosphere at 700 ℃ to obtain tungsten-zirconium composite oxide;
step 2, respectively weighingTaking and measuring tungsten-zirconium composite oxide and melamine (C)3N6H6) And trichloro-s-triazine (C)3N3Cl3) Wherein melamine (C)3N6H6) And trichloro-s-triazine (C)3N3Cl3) In a molar ratio of 2:1, fully grinding and mixing, tabletting and forming, putting the obtained sample in a tube furnace, introducing high-purity nitrogen with the flow of 100ml/min, heating to 600 ℃ at the speed of 2 ℃/min, keeping the temperature for 4 hours, and cooling to room temperature to obtain a carbon nitride modified tungsten-zirconium composite oxide sample;
step 3, accurately measuring H with certain concentration2PtCl6Weighing and soaking a measured carbon nitride modified tungsten-zirconium composite oxide carrier in the aqueous solution, standing for 24 hours, drying at 110 ℃, and dechlorinating to obtain the carbon nitride modified tungsten-zirconium composite oxide platinum-supported catalyst (Pt/C)3N4@WO3/ZrO2) Wherein the Pt content is 2 wt%; graphite phase C3N4The content is 0.1 wt%; WO3The balance being ZrO, the content being 12 wt%2。
The atomic ratio of nitrogen to carbon is close to 4:3 and is C according to the elemental analysis data of the sample3N4The composition ratio of (A); and identified as graphitic carbon nitride in combination with the diffuse-raman spectral data.
Application test:
3.5 g of Pt/C3N4@WO3/ZrO2The catalyst is placed in a fixed bed reactor with a flow rate of
The catalyst was reduced with 150ml/min pure hydrogen at 200 ℃ for 2 h. Introducing 40% glycerol aqueous solution, wherein the mass space velocity of glycerol is 0.2h-1The hydrogen flow is controlled to be 150ml/min, the reaction temperature is 150 ℃, and the reaction pressure is 4 MPa. During the reaction, samples were taken every 5h and analyzed in a gas chromatograph, and the experimental results are shown in table 1.
TABLE 1 Glycerol hydrogenation performance of the catalyst of this example
| Time per hour | Glycerol conversion/% | 1, 3-propanediol yield/%) |
| 50 | 68.8 | 35.7 |
| 100 | 67.7 | 35.1 |
| 150 | 66.3 | 34.3 |
| 200 | 64.2 | 33.3 |
Note: in the tables of the present invention, the conversion of glycerin and the yield of 1, 3-propanediol were calculated from the gas chromatography analysis of the reaction product. Glycerol conversion rate ═ amount of glycerol converted/amount of fed glycerol × 100%; the yield of 1, 3-propanediol is equal to the amount of 1, 3-propanediol in the product/theoretically the amount of glycerol converted into 1, 3-propanediol overall x 100%.
Example 2
This example provides a metal/solid acid catalyst (Pt/C)3N4@WO3/ZrO2) The preparation was carried out analogously to example 1, the amounts of the constituents differing essentially. Specifically, the Pt/C prepared in this example3N4@WO3/ZrO2Catalyst (Pt content 2.0 wt%; graphite phase C)3N4The content is 0.2 wt%;WO3the content is 12 wt%; the balance being ZrO2)。
The catalyst was tested under the same test conditions as in example 1 and the results are shown in table 2.
TABLE 2 Glycerol hydrogenation performance of the catalyst of this example
| Time per hour | Glycerol conversion/% | 1, 3-propanediol yield/%) |
| 50 | 70.8 | 36.8 |
| 100 | 70.3 | 36.6 |
| 150 | 69.3 | 36.1 |
| 200 | 69.2 | 36.0 |
Example 3
This example provides a metal/solid acid catalyst (Pt/C)3N4@WO3/ZrO2) The preparation was carried out analogously to example 1, the amounts of the constituents differing essentially. Specifically, the Pt/C prepared in this example3N4@WO3/ZrO2Catalyst (Pt content 2.0 wt%; graphite phase C)3N4The content is 0.5 wt%; WO3The content is 12 wt%; the balance being ZrO2)。
The catalyst was tested using the same test conditions as in example 1 and the results are shown in table 3.
TABLE 3 Glycerol hydrogenation performance of the catalyst of this example
| Time per hour | Glycerol conversion/% | 1, 3-propanediol yield/%) |
| 50 | 72.8 | 37.7 |
| 100 | 72.7 | 37.6 |
| 150 | 72.3 | 37.2 |
| 200 | 72.2 | 37.4 |
Example 4
This example provides a metal/solid acid catalyst (Pt/C)3N4@WO3/ZrO2) Preparation ofThe procedure is similar to example 1, mainly with different contents of components. Specifically, the Pt/C prepared in this example3N4@WO3/ZrO2Catalyst (Pt content 2.0 wt%; graphite phase C)3N4The content is 0.8 wt%; WO3The content is 12 wt%; the balance being ZrO2)。
The catalyst was tested using the same test conditions as in example 1 and the results are shown in table 4.
TABLE 4 Glycerol hydrogenation performance of the catalyst of this example
| Time per hour | Glycerol conversion/% | 1, 3-propanediol yield/%) |
| 50 | 50.8 | 26.3 |
| 100 | 50.7 | 26.4 |
| 150 | 50.3 | 26.2 |
| 200 | 50.5 | 26.3 |
Example 5
This example provides a metal/solid acid catalyst (Pt/C)3N4@WO3/ZrO2) The preparation was carried out analogously to example 1, the amounts of the constituents differing essentially. Specifically, the Pt/C prepared in this example3N4@WO3/ZrO2Catalyst (Pt content 1.0 wt%; graphite phase C)3N4The content is 0.5 wt%; WO3The content is 12 wt%; the balance being ZrO2)。
The catalyst was tested using the same test conditions as in example 1 and the results are shown in table 5.
TABLE 5 Glycerol hydrogenation performance of the catalyst of this example
| Time per hour | Glycerol conversion/% | 1, 3-propanediol yield/%) |
| 50 | 39.8 | 20.7 |
| 100 | 39.5 | 20.5 |
| 150 | 39.3 | 20.4 |
| 200 | 39.3 | 20.4 |
Example 6
This example provides a metal/solid acid catalyst (Pt/C)3N4@WO3/Al2O3) The preparation process was similar to that of example 1, except that alumina was used instead of zirconia (the solid acid was a tungsten-aluminum composite oxide), and the contents of the components were different. Specifically, the Pt/C prepared in this example3N4@WO3/Al2O3Catalyst (Pt content 2.0 wt%; graphite phase C)3N4The content is 0.5 wt%; WO3The content is 12 wt%; the balance being Al2O3)。
The above catalysts were tested under the same test conditions as in example 1 and the results are shown in Table 6.
TABLE 6 Glycerol hydrogenation performance of the catalyst of this example
| Time per hour | Glycerol conversion/% | 1, 3-propanediol yield/%) |
| 50 | 64.5 | 32.3 |
| 100 | 64.5 | 32.3 |
| 150 | 64.3 | 32.2 |
| 200 | 64.3 | 32.2 |
Comparative example 1
This comparative example provides an application comparative experiment using a prior art catalyst, specifically:
platinum on tungsten zirconium composite oxide (Pt/WO)3/ZrO2) A catalyst, wherein the Pt content is 2 wt%; WO3The balance being ZrO, the content being 12 wt%2. Compared with the preparation process of the example 1, the carbon nitride modification step is not mainly carried out. The above catalysts were tested under the same test conditions as in example 1 and the results are shown in Table 7.
TABLE 7 Glycerol hydrogenation reaction Performance of the catalyst of this comparative example
| Time per hour | Glycerol conversion/% | 1, 3-propanediol yield/%) |
| 50 | 62.5 | 26.7 |
| 100 | 55.7 | 26.4 |
| 150 | 45.3 | 24.2 |
| 200 | 38.2 | 22.9 |
Comparative example 2
This comparative example provides an application comparative experiment using a prior art catalyst, specifically:
platinum on tungsten zirconium composite oxide (Pt/WO)3/Al2O3) A catalyst, wherein the Pt content is 2 wt%; WO312 wt% of Al for the remainder2O3. Compared with the preparation process of the example 6, the carbon nitride modification step is not carried out. The above catalysts were tested under the same test conditions as in example 6, and the results are shown in Table 8.
TABLE 8 Glycerol hydrogenation reaction Performance of the catalyst of this comparative example
| Time per hour | Glycerol conversion/% | 1, 3-propanediol yield/%) |
| 50 | 68.5 | 34.1 |
| 100 | 66.5 | 33.6 |
| 150 | 60.5 | 31.5 |
| 200 | 57.8 | 30.3 |
Note: for the catalyst taking the tungsten-zirconium composite oxide as the carrier, the modification of carbon nitride slightly reduces the initial activity of the catalyst, but obviously improves the stability of the catalyst.
As can be seen from the above examples and comparative example data, the metal/solid acid catalyst containing graphite-phase carbon nitride provided by the invention has good stability under hydrothermal conditions, and is obviously superior to the sample without carbon nitride modification.
Claims (13)
1. A metal/solid acid catalyst for preparing 1, 3-propylene glycol by glycerol hydrogenation, wherein the metal/solid acid catalyst contains a solid acid surface modifier graphite phase carbon nitride, and the content of the graphite phase carbon nitride in the metal/solid acid catalyst is 0.01-3 wt%;
in the metal/solid acid catalyst, the active metal is platinum; the solid acid is tungsten-aluminum composite oxide or tungsten-zirconium composite oxide.
2. The metal/solid acid catalyst for the hydrogenation of glycerol to produce 1, 3-propanediol according to claim 1, wherein the amount of graphite-phase carbon nitride in the metal/solid acid catalyst is from 0.05 wt% to 2 wt%.
3. The metal/solid acid catalyst for the hydrogenation of glycerol to produce 1, 3-propanediol according to claim 2, wherein the amount of graphite-phase carbon nitride in the metal/solid acid catalyst is from 0.1 wt% to 1 wt%.
4. The metal/solid acid catalyst for the hydrogenation of glycerol to produce 1, 3-propanediol according to claim 1, wherein the content of active metal in said metal/solid acid catalyst is 0.5-3 wt%.
5. The metal/solid acid catalyst for the hydrogenation of glycerol to produce 1, 3-propanediol according to claim 1, wherein in said metal/solid acid catalyst, the active metal is platinum and the solid acid is a tungsten-aluminum composite oxide or a tungsten-zirconium composite oxide; 1 to 2 weight percent of platinum, 0.5 to 1 weight percent of graphite phase carbon nitride, 10 to 15 weight percent of tungsten oxide and the balance of zirconium oxide or aluminum oxide.
6. A process for preparing a metal/solid acid catalyst according to any one of claims 1 to 5, wherein the process comprises surface modification of the solid acid by in situ formation of graphite phase carbon nitride followed by active metal loading.
7. The method of preparing a metal/solid acid catalyst according to claim 6, wherein the step of surface-modifying the solid acid in a manner to generate graphite-phase carbon nitride in situ comprises:
firstly, mixing the solid acid with the raw material for preparing the graphite-phase carbon nitride, and then roasting to generate the graphite-phase carbon nitride on the surface of the solid acid, thereby realizing the surface modification of the solid acid.
8. The method for producing a metal/solid acid catalyst according to claim 7, wherein in the step of mixing the solid acid with the raw material for producing the graphite-phase carbon nitride, the mixing is a grinding mixing.
9. The method of preparing a metal/solid acid catalyst according to claim 7, wherein the raw material for preparing the graphite-phase carbon nitride comprises a carbon-nitrogen source:
the carbon-nitrogen source is a mixture of melamine and trichloro-s-triazine, or dicyandiamide.
10. The method of claim 9, wherein the mixture comprises melamine and trichloro-s-triazine in a molar ratio of (1-4) to 1.
11. The method of claim 10, wherein the mixture comprises melamine and trichloro-s-triazine in a molar ratio of 2: 1.
12. The method of claim 7, further comprising the step of tabletting the mixed material before the calcination treatment.
13. The method for preparing a metal/solid acid catalyst according to claim 7, wherein the conditions of the calcination treatment are: keeping the temperature at 500-650 ℃ for 2-6 hours.
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| CN115634688A (en) * | 2021-07-20 | 2023-01-24 | 中国石油天然气股份有限公司 | Platinum Metal/WO 3 -ZrO 2 -M x O y Catalyst, preparation method and application thereof |
| CN116655450A (en) * | 2022-02-17 | 2023-08-29 | 张家港美景荣化学工业有限公司 | Method and device for producing by-product propanol by converting glycerol into polyalcohol |
| CN117861676A (en) * | 2022-10-10 | 2024-04-12 | 中国石油化工股份有限公司 | Double-catalytic center catalyst, preparation method and application thereof, and preparation method of dihydric alcohol |
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