CN102294240B - Pd/C catalyst for producing 2,3,5-trimethylhydroquinone (TMHQ) by virtue of hydrogenation of 2,3,5-trimethylbenzoquinone (TMBQ) and preparation method thereof - Google Patents
Pd/C catalyst for producing 2,3,5-trimethylhydroquinone (TMHQ) by virtue of hydrogenation of 2,3,5-trimethylbenzoquinone (TMBQ) and preparation method thereof Download PDFInfo
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 162
- 239000003054 catalyst Substances 0.000 title claims abstract description 95
- QIXDHVDGPXBRRD-UHFFFAOYSA-N 2,3,5-trimethylcyclohexa-2,5-diene-1,4-dione Chemical compound CC1=CC(=O)C(C)=C(C)C1=O QIXDHVDGPXBRRD-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 31
- AUFZRCJENRSRLY-UHFFFAOYSA-N 2,3,5-trimethylhydroquinone Chemical compound CC1=CC(O)=C(C)C(C)=C1O AUFZRCJENRSRLY-UHFFFAOYSA-N 0.000 title abstract 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 79
- 238000000034 method Methods 0.000 claims abstract description 20
- 230000009467 reduction Effects 0.000 claims abstract description 19
- 239000002253 acid Substances 0.000 claims abstract description 16
- 239000008367 deionised water Substances 0.000 claims abstract description 12
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 9
- 238000010306 acid treatment Methods 0.000 claims abstract description 8
- 230000007935 neutral effect Effects 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- 239000002105 nanoparticle Substances 0.000 claims abstract description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 54
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 17
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 15
- 229910052763 palladium Inorganic materials 0.000 claims description 13
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- 239000010970 precious metal Substances 0.000 claims description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 7
- 229910052801 chlorine Inorganic materials 0.000 claims description 7
- 239000000460 chlorine Substances 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 239000002250 absorbent Substances 0.000 claims description 6
- 230000002745 absorbent Effects 0.000 claims description 6
- 239000003610 charcoal Substances 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- 235000006408 oxalic acid Nutrition 0.000 claims description 5
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 4
- 244000060011 Cocos nucifera Species 0.000 claims description 4
- 239000010903 husk Substances 0.000 claims description 4
- -1 palladium amine Chemical class 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 239000004280 Sodium formate Substances 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims description 3
- 235000019254 sodium formate Nutrition 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 21
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 6
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 abstract description 2
- 229910000510 noble metal Inorganic materials 0.000 abstract description 2
- 239000012018 catalyst precursor Substances 0.000 abstract 3
- 239000006185 dispersion Substances 0.000 abstract 1
- 230000008595 infiltration Effects 0.000 abstract 1
- 238000001764 infiltration Methods 0.000 abstract 1
- 238000010992 reflux Methods 0.000 abstract 1
- GVJHHUAWPYXKBD-UHFFFAOYSA-N (±)-α-Tocopherol Chemical compound OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 description 20
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- 230000000694 effects Effects 0.000 description 16
- 238000006722 reduction reaction Methods 0.000 description 13
- 238000004519 manufacturing process Methods 0.000 description 11
- 229930003427 Vitamin E Natural products 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 10
- WIGCFUFOHFEKBI-UHFFFAOYSA-N gamma-tocopherol Natural products CC(C)CCCC(C)CCCC(C)CCCC1CCC2C(C)C(O)C(C)C(C)C2O1 WIGCFUFOHFEKBI-UHFFFAOYSA-N 0.000 description 10
- 235000019165 vitamin E Nutrition 0.000 description 10
- 229940046009 vitamin E Drugs 0.000 description 10
- 239000011709 vitamin E Substances 0.000 description 10
- 101150003085 Pdcl gene Proteins 0.000 description 9
- 238000002803 maceration Methods 0.000 description 7
- 239000000376 reactant Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 6
- 238000004448 titration Methods 0.000 description 6
- 239000003513 alkali Substances 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 239000012298 atmosphere Substances 0.000 description 5
- 238000007598 dipping method Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- 238000007605 air drying Methods 0.000 description 4
- 239000003638 chemical reducing agent Substances 0.000 description 4
- 239000002808 molecular sieve Substances 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 229940052881 quinhydrone Drugs 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 238000006277 sulfonation reaction Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000006424 Flood reaction Methods 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- RXKJFZQQPQGTFL-UHFFFAOYSA-N dihydroxyacetone Chemical compound OCC(=O)CO RXKJFZQQPQGTFL-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000009904 heterogeneous catalytic hydrogenation reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 1
- 229940100630 metacresol Drugs 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- BDJXVNRFAQSMAA-UHFFFAOYSA-N quinhydrone Chemical compound OC1=CC=C(O)C=C1.O=C1C=CC(=O)C=C1 BDJXVNRFAQSMAA-UHFFFAOYSA-N 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
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Abstract
The invention relates to a Pd/C catalyst for producing 2,3,5-trimethylhydroquinone (TMHQ) by virtue of hydrogenation of 2,3,5-trimethylbenzoquinone (TMBQ) and a preparation method thereof. In the Pd/C catalyst provided by the invention, a noble metal Pd supported on a carrier activated carbon exists in a nano particle form, the dispersion degree of Pd is not less than 30%, and the carrier activated carbon has micropores and mesopores. The preparation method comprises the following steps: (1) carrying out acid treatment on the carrier activated carbon, and adding an acid solution in activated carbon for carrying out water bath reflux treatment; (2) washing activated carbon treated by the acid with deionized water to be neutral, and drying so as to obtain the activated carbon carrier; (3) infiltrating the activated carbon carrier with an infiltration liquid in advance; (4) slowly dropwise adding a 0.01-0.3mol/L Pd source solution in the activated carbon carrier which is infiltrated in advance, so that Pd is supported on the activated carbon, thus a catalyst precursor is obtained; and (5) drying the catalyst precursor and then treating the dried catalyst precursor by a reduction method so as to obtain the Pd/C catalyst for producing TMHQ by virtue of hydrogenation of TMBQ. The Pd/C catalyst provided by the invention has the characteristics of being simple and efficient, and having high catalysis property in BTOP (benzene to phenol) reaction.
Description
Technical field
The present invention relates to a kind of loaded noble metal catalyst for liquid phase catalytic hydrogenation reaction and preparation method thereof, particularly relate to a kind of for TMBQ (2,3,5-trimethylbenzoquinoe) hydrogenation production TMHQ (2,3,5-TMHQ) Pd/C catalyst and preparation method.
Background technology
Vitamin E (VE) not only should be used as the additive of medicine, health products, food, cosmetics, and more and more as industrial antioxidant, becomes in recent years the focus product that receives much attention.The domestic and international market sharply increases the demand of VE, and price constantly rises, thereby the production of in good time operation and expansion VE all can bring preferably economic benefit.
TMHQ (TMHQ) is a kind of organic substance of white powder, is the important intermediate of synthesising complex E, and VE is synthesized in itself and different vegetable alcohol reaction.But the production technology of this class intermediate by the monopolization of external major company, so that the production of China VE is subjected to the restriction of raw material and intermediate, is lacked competitiveness always in the international market for a long time.Although in recent years, the domestic unit develops such as Zhejiang chemical research institute the synthetic TMHQ technology of metacresol method, promoted the production of China VE, but because this technological development ground zero, technical advance is compared with external similar enterprise with maturity and is had obvious gap.Therefore, further carry out the study on the synthesis of TMHQ significant to the production of domestic VE.
The method of synthetic TMHQ mainly contains chemical reduction method and catalytic hydrogenating reduction method take TMBQ as raw material.Chemical reduction method generally is with raw material 2,3, and 6-trimethyl phenol (TMP) earlier sulfonation generates 4-sulfonic group-2,3,6-TMP, then through oxidant (such as MnO
2) oxidation generation TMBQ, then be reduced to TMHQ through reducing agent (such as sodium hydrosulfite).China enterprise adopts this production technology to produce TMHQ basically.In actual production, the solid 4-sulfonic group-2,3,6-TMP that generates after the TMP sulfonation tends to caking, uses MnO
2Dissolution of solid that must these are block before the oxidation, complex operation is time-consuming.In addition, reduction process not only produces a large amount of waste liquids, and unavoidably introduces impurity and cause the TMHQ quality to reduce.The catalytic hydrogenation method refers in hydrogen atmosphere, under the catalyst action, TMBQ is carried out the process that the hydrogenation reaction direct-reduction becomes TMHQ, and this method has the characteristics such as product quality is high, cost is low, is the production method that at present external major company generally adopts.
Because VE is mainly used in medicine and food additives field, as the important source material TMHQ that produces VE, its production purity affects the Performance and quality of downstream product.Prepare the TMHQ process based on the TMBQ catalytic hydrogenating reduction, present difficulty is in suitable solvent, develops the effective catalyst that a kind of TMBQ orientation changes into TMHQ.
US Patent No. 3839468 has been investigated under the catalyst based effect of Pd, and solvent becomes the impact of TMHQ on the TMBQ hydrogenating reduction.Discovery is with C
3-C
5Alcohol is as solvent, and product is colored (air oxidation) degree and is lower than with C
1-C
2Alcohol is the situation of solvent, and painted is formation quinhydrone compound because TMBQ and TMHQ mutually combine, and quinhydrone is black when solid state, makes TMHQ painted just because of the existence of this material.With aliphatic ketone (C
3-C
6) during as solvent, the catalyst based life-span of Pd is prolonged, and TMHQ purity is higher.US Patent No. 4769500 is mentioned the heterogeneous catalytic hydrogenation catalyst that a kind of precious metals pd loads to the alkali metal containing alumino-silicate, under normal pressure, 40 ℃ of reaction temperatures, what the conversion ratio of TMBQ reached 100%, TMHQ selectively also is higher than 99%, and catalyst can be reused.But this patent does not have structure and concrete composition of clear and definite carrier alumino-silicate, does not mention the concrete preparation process of catalyst yet.
Because catalytic hydrogenation reaction is to carry out on the surface of metal Pd, therefore usually for the identical catalyst of precious metals pd load capacity, the decentralization of Pd is higher in the catalyst, and activity is then higher.If directly that the Pd compound is (sour such as the chlorine palladium, or chlorine palladium acid sodium) solution loads on the active carbon, very thin glossiness metal Pd layer can appear in activated carbon surface very soon, this mainly is that these groups are easy to make the Pd cation to be reduced into the metal Pd of zeroth order because activated carbon surface contains the oxy radicals such as hydroxyl, aldehyde radical.Therefore, the decentralization of precious metals pd is generally all very low in the catalyst that so prepares.One of effective ways that overcome this technical problem are that the Pd ion that will contain in the maceration extract of Pd compound before dipping is transformed into insoluble compound.For example, at room temperature the water soluble compound hydrolysis of Pd is become insoluble Pd (OH)
2Or PdO, and then load on the active carbon, then with the reducing agent reduction, can prevent that like this migration of Pd and particle from growing up.US Patent No. 3138560 adds hydrogen peroxide in maceration extract makes the water soluble compound hydrolysis of Pd generate insoluble compound, then floods.But because hydrogen peroxide itself also has oxidisability, can be with the Surface Groups of Active Carbons oxidation, thus will change the physico-chemical property of carrier surface, namely change the surface group structure of carrier, thereby catalyst is caused uncertain negative effect.The maceration extract that contains the Pd compound is prepared in 4476242 propositions of US Patent No. with organic matters such as methyl alcohol or pyridines; this grows up very effective to the migration and the particle that suppress Pd; but preparation process is used methyl alcohol or this harmful compound of pyridine, is disadvantageous from the angle of environmental protection.In addition, European patent EP 08150726.1 has been reported under the effect of surfactant, the Pd cation is reduced into the colloidal sol of zero-valent metal Pd by regulating the pH value, load to again preparation Pd/C catalyst on the active carbon, but because colloidal stability is not high, cause Pd to be difficult to be evenly distributed at carrier active carbon, thereby cause the decentralization of Pd to reduce.
In sum, although existing Pd/C catalyst can show high selectivity, it is low that it exists the precious metals pd decentralization, the not high weak point of catalytic activity in the process of the synthetic TMHQ of catalysis TMBQ hydrogenation.
Summary of the invention
The present invention is directed to the existing precious metals pd decentralization of existing Pd/C catalyst low, the not high weak point of catalytic activity in the process of the synthetic TMHQ of catalysis TMBQ hydrogenation, provide a kind of precious metals pd decentralization high, produce in the TMHQ process at the TMBQ catalytic hydrogenation and not only to have high selectivity, and in the TMBQ catalytic hydrogenation reaction, have a high catalytic activity be used for TMBQ (2,3, the 5-trimethylbenzoquinone) hydrogenation is produced TMHQ (2,3,5-TMHQ) Pd/C catalyst and preparation method.
The present invention finishes by following technical scheme, a kind of Pd/C catalyst of producing TMHQ for the TMBQ hydrogenation, the precious metals pd that wherein is carried on the carrier active carbon exists with nanoparticle form, the Pd decentralization is not less than 30%, carrier active carbon is coconut husk type active carbon, have micropore and mesoporous on the carrier active carbon, its intermediary hole pore volume is 5～6 times of micropore pore volume.
At described a kind of Pd/C catalyst of producing TMHQ for the TMBQ hydrogenation, the Pd nano-particles size is 2.0～5.0nm.
At described a kind of Pd/C catalyst of producing TMHQ for the TMBQ hydrogenation, the specific area of described carrier active carbon is greater than 1000m
2/ g, the mesoporous 2～10nm that is of a size of on the carrier active carbon.
A kind of preparation method who produces the Pd/C catalyst of TMHQ for the TMBQ hydrogenation of the present invention may further comprise the steps:
(1) acid treatment of carrier active carbon adds acid solution in the active carbon, and water-bath reflow treatment 2～4h, acid solution adopt a kind of in hydrochloric acid, phosphoric acid or the salpeter solution;
(2) with deionized water that the active carbon cyclic washing of above-mentioned acid treatment is extremely neutral, in 80～120 ℃ of drying 0.5～10h, get pretreated absorbent charcoal carrier;
(3) pretreated carried by active carbon body and function infiltrate is infiltrated 0.2～5h in advance, the concentration of infiltrate is 0.1～2mol/L, and the infiltrate quality is 0～4 with the ratio of quality of activated carbon;
(4) be that the Pd source solution of 0.01～0.3mol/L is added drop-wise in the absorbent charcoal carrier that infiltrates in advance lentamente with concentration, Pd is carried on the active carbon, namely obtain catalyst precarsor, wherein the quality of metal Pd adding is counted 1.0～5.0wt.% by the catalyst gross mass;
(5) adopt after drying method of reducing to process catalyst precarsor, namely obtain producing for the TMBQ hydrogenation Pd/C catalyst of TMHQ.
In described a kind of preparation method who produces the Pd/C catalyst of TMHQ for the TMBQ hydrogenation, the concentration of used acid solution is 5wt.%～10wt.% in step (1).
In described a kind of preparation method who produces the Pd/C catalyst of TMHQ for the TMBQ hydrogenation, the granularity of carrier active carbon is 180～220 orders, preferred 200 orders.
In described a kind of preparation method who produces the Pd/C catalyst of TMHQ for the TMBQ hydrogenation, be preferably 0.5～4h the drying time after the carrier active carbon acid treatment.
In described a kind of preparation method who produces the Pd/C catalyst of TMHQ for the TMBQ hydrogenation, used infiltrate is a kind of in sodium carbonate liquor or the oxalic acid solution in step (3).
In described a kind of preparation method who produces the Pd/C catalyst of TMHQ for the TMBQ hydrogenation, the Pd source of used Pd source solution is a kind of in acetate, nitrate, hydrochloride, the acid of chlorine palladium, palladium amine complex or the organic palladium of Pd in step (4), a kind of in preferred chlorine palladium acid or the chlorine palladium acid sodium.
In described a kind of preparation method who produces the Pd/C catalyst of TMHQ for the TMBQ hydrogenation, used method of reducing is a kind of in hydrogen reducing, formaldehyde reduction, reduction of ethylene glycol, formic acid reduction, the sodium formate reduction in step (5), a kind of in preferred hydrogen reducing or the formaldehyde reduction.
The present invention compares with the method for the existing Pd/C of preparation catalyst, characteristics of the present invention are: the present invention is before dipping Pd compound, carrier active carbon is after sour preliminary treatment, having added suitable infiltrate modifies, since infiltrate can with carrier active carbon on oxy radical interact, improved the reduction potential of carrier.When Pd loaded on the active carbon, the Pd cation just can not reduced by the carrier surface group of modified, thereby Pd can be distributed in the surface of carrier active carbon very equably.In addition, the present invention also has: the precious metals pd catalyst of preparation has that decentralization is high, the Pd nano particle is even, used carrier infiltrate wide material sources, cheap, catalyst preparation process is simple, and the catalyst of preparation has the outstanding feature of very high catalytic activity in the TMBQ catalytic hydrogenation reaction.
Among the present invention, the decentralization of precious metals pd that adopted CO pulse titration measuring, decentralization calculates by following formula:
Decentralization=(V
Inhale* M
Pd)/(22400 * W
Pd) * 100%
In the formula: V
InhaleCO adsorbance (ml) under the expression standard state,
M
PdAtomic weight 106.4gmol for Pd
-1,
W
PdBe Pd quality (g) in the catalyst.
Among the present invention, the precious metals pd particle size of prepared Pd/C catalyst adopts transmission electron microscope (TEM) technology to analyze.
Catalyst activity appreciation condition: reactant TMBQ:10～20g; The ratio that catalyst amount accounts for reactant is 0.05～0.12wt.%; Reaction dissolvent ethyl acetate: 35～65ml; Hydrogen initial pressure: 0.5～0.8MPa; Reaction temperature: 65～95 ℃.
Measure the still internal pressure and reduce 0.1MPa Δ t of needed time, with initial hydrogen-absorption speed
The TMBQ hydrogenation activity of evaluate catalysts.
Characteristics of the present invention are: by changing the alkali treatment condition, such as NaOH concentration, temperature and time etc., can change micropore in the microporous mesoporous composite molecular sieve catalyst of Fe-ZSM-5 and mesoporous ratio, thus the catalytic performance of catalyst in BTOP before and after the modulation alkali treatment.Sign and reaction evaluating result from sample, the mode of the present invention by alkali treatment is with in the mesoporous introducing micropore Fe-ZSM-5 molecular sieve crystal, the gained sample topography is complete, crystal structure is constant, and the molecular sieve mass-transfer performance significantly improves, and its catalytic activity and stability in the BTOP catalytic reaction also are significantly improved.Under the alkali treatment condition of optimizing, the catalyst after the modification reacts 3h under 320 ℃ of reaction temperatures, and the conversion ratio of benzene still maintains 20%, apparently higher than the catalytic activity without the alkali treatment sample, and under reaction condition phenol selectively reach 100%.Compared with prior art, the present invention is to provide a kind of simply, effectively, in the BTOP reaction, have the microporous mesoporous compound Fe-ZSM-5 zeolite molecular sieve catalyst preparation method of high catalytic performance.
Description of drawings
Fig. 1 is TEM figure and the particle diameter distribution map thereof of 5wt.%Pd/C catalyst among the embodiment 1.
Fig. 2 is TEM figure and the particle diameter distribution map thereof of 2wt.%Pd/C catalyst among the embodiment 4.
The specific embodiment
Below by embodiment the present invention is made further and to specify, but the present invention is not limited to following example.
Embodiment 1
20g is Powdered, and specific area is greater than 1000m
2The coconut husk type active carbon concentration of/g is 60 ℃ of lower water-bath backflow 2h of nitric acid of 5wt.%, then uses the deionized water cyclic washing to neutral, and is for subsequent use in 80 ℃ of lower forced air drying 4h.
The preparation of Pd source maceration extract takes by weighing the approximately PdCl about 3g
2Solid joins in the 7.29ml concentrated hydrochloric acid, adds until completely dissolved deionized water and is diluted in the volumetric flask of 50ml for subsequent use.
Get pretreated active carbon 3g, adding 10ml concentration is that the sodium carbonate of 0.9mol/L infiltrates active carbon 0.5h in advance.Load capacity according to Pd is 5.0wt.%, pipettes PdCl
2Solution is 14ml approximately, adds in the active carbon that infiltrates in advance behind the dipping 6h, after then putting into 50 ℃ of baking ovens and spending the night, in 10vol.%H
2(overall flow rate: 30ml/min) the lower 200 ℃ of reductase 12 h of atmosphere get catalyst to/Ar, by CO pulse titration catalyst are carried out decentralization and characterize, and by analysis, its decentralization is 50%.
Catalyst activity appreciation condition: reactant TMBQ:15g; Reaction dissolvent ethyl acetate: 50ml; Hydrogen initial pressure: 0.6MPa; Reaction temperature: 80 ℃; Catalyst: 0.012g.
The catalyst activity evaluation result: it is 4.5min that record reduces the 0.1MPa required time, and its hydrogen-absorption speed is 648ml (min g)
-1
Embodiment 2
20g is Powdered, and specific area is greater than 1000m
2The active carbon concentration of/g is 60 ℃ of lower water-bath backflow 2h of nitric acid of 5wt.%, then uses the deionized water cyclic washing to neutral, and is for subsequent use in 80 ℃ of lower forced air drying 4h.
The preparation of Pd source maceration extract takes by weighing the approximately PdCl about 3g
2Solid joins in the 7.29ml concentrated hydrochloric acid, adds until completely dissolved deionized water and is diluted in the volumetric flask of 50ml for subsequent use.
Get pretreated active carbon 3g, adding 10ml concentration is that the oxalic acid of 0.1mol/L infiltrates active carbon 0.5h in advance.Load capacity according to Pd is 5.0wt%, pipettes PdCl
2Solution is 14ml approximately, adds in the active carbon that infiltrates in advance behind the dipping 6h, after then putting into 50 ℃ of baking ovens and spending the night, in 10vol.%H
2(overall flow rate: 30ml/min) the lower 200 ℃ of reductase 12 h of atmosphere get catalyst to/Ar, by CO pulse titration catalyst are carried out decentralization and characterize, and by analysis, its decentralization is 45%.
Catalyst activity appreciation condition: reactant TMBQ:15g; Reaction dissolvent ethyl acetate: 50ml; Hydrogen initial pressure: 0.6MPa; Reaction temperature: 80 ℃; Catalyst: 0.012g.
The catalyst activity evaluation result: it is 4.9min that record reduces the 0.1MPa required time, and its hydrogen-absorption speed is 595ml (min g)
-1
Embodiment 3
20g is Powdered, and specific area is greater than 1000m
2The coconut husk type active carbon concentration of/g is 60 ℃ of lower water-bath backflow 2h of nitric acid of 10wt.%, then uses the deionized water cyclic washing to neutral, and is for subsequent use in 80 ℃ of lower forced air drying 4h.
The preparation of Pd source maceration extract takes by weighing the approximately PdCl about 3g
2Solid joins in the 7.29ml concentrated hydrochloric acid, adds until completely dissolved deionized water and is diluted in the volumetric flask of 50ml for subsequent use.
Get pretreated active carbon 3g, adding 10ml concentration is that the oxalic acid of 0.1mol/L infiltrates active carbon 0.5h in advance.Load capacity according to Pd is 5.0wt%, pipettes PdCl
2Solution is 14ml approximately, adds in the active carbon that infiltrates in advance behind the dipping 6h, after then putting into 50 ℃ of baking ovens and spending the night, in 10vol.%H
2(overall flow rate: 30ml/min) the lower 200 ℃ of reductase 12 h of atmosphere get catalyst to/Ar, by CO pulse titration catalyst are carried out decentralization and characterize, and by analysis, its decentralization is 43%.
Catalyst activity appreciation condition: reactant TMBQ:15g; Reaction dissolvent ethyl acetate: 50ml; Hydrogen initial pressure: 0.6MPa; Reaction temperature: 80 ℃; Catalyst: 0.012g.
The catalyst activity evaluation result: it is 10.5min that record reduces the 0.1MPa required time, and its hydrogen-absorption speed is 648ml (min g)
-1
Embodiment 4
20g is Powdered, and specific area is greater than 1000m
2The active carbon concentration of/g is 60 ℃ of lower water-bath backflow 2h of nitric acid of 10wt.%, then uses the deionized water cyclic washing to neutral, and is for subsequent use in 80 ℃ of lower forced air drying 4h.
The preparation of Pd source maceration extract takes by weighing the approximately PdCl about 3g
2Solid joins in the 7.29ml concentrated hydrochloric acid, adds until completely dissolved deionized water and is diluted in the volumetric flask of 50ml for subsequent use.
Get pretreated active carbon 3g, adding 2.8ml concentration is 1.62mol/L Na
2CO
3Stir.Load capacity according to Pd is 2.0wt%, pipettes PdCl
2Solution is 1ml approximately, simultaneously to thin up PdCl wherein
2Behind the solution, add in the active carbon that infiltrates in advance and flood 6h, after then putting into 50 ℃ of baking ovens and spending the night, in 10vol.%H
2(overall flow rate: 30ml/min) the lower 200 ℃ of reductase 12 h of atmosphere get catalyst to/Ar, by CO pulse titration catalyst are carried out decentralization and characterize, and by analysis, its decentralization is 35%.
Catalyst activity appreciation condition: reactant TMBQ:15g; Reaction dissolvent ethyl acetate: 50ml; Hydrogen initial pressure: 0.6MPa; Reaction temperature: 80 ℃; Catalyst: 0.012g.
The catalyst activity evaluation result: it is 6.2min that record reduces the 0.1MPa required time, and its hydrogen-absorption speed is 470ml (min g)
-1
Comparative example 1
5.0wt.%Pd/C catalyst from domestic Pd/C Catalyst Production producer buys carries out decentralization by CO pulse titration to catalyst and characterizes, and by analysis, its decentralization is 26%.
Catalyst activity appreciation condition: reactant TMBQ:15g; Reaction dissolvent ethyl acetate: 50ml; Hydrogen initial pressure: 0.6MPa; Reaction temperature: 80 ℃; Catalyst: 0.012g.
The catalyst activity evaluation result: it is 11.5mm that record reduces the 0.1MPa required time, and its hydrogen-absorption speed is 254ml (min g)
-1
Claims (8)
1. one kind is used for the Pd/C catalyst that the TMBQ hydrogenation is produced TMHQ, it is characterized in that the precious metals pd that described Pd/C catalyst wherein is carried on the carrier active carbon exists with nanoparticle form, the Pd decentralization is not less than 30%, carrier active carbon is coconut husk type active carbon, has micropore and mesoporous on the carrier active carbon, its intermediary hole pore volume is 5 ~ 6 times of micropore pore volume, and the Pd nano-particles size is 2.0 ~ 5.0 nm, and the specific area of carrier active carbon is greater than 1000 m
2/ g, mesoporous 2 ~ 10 nm that are of a size of on the carrier active carbon.
2. according to a kind of preparation method who produces the Pd/C catalyst of TMHQ for the TMBQ hydrogenation claimed in claim 1, it is characterized in that this preparation method may further comprise the steps:
⑴ the acid treatment of carrier active carbon adds acid solution in the active carbon, and water-bath reflow treatment 2～4 h, acid solution adopt a kind of in hydrochloric acid, phosphoric acid or the salpeter solution;
⑵ extremely neutral with the active carbon cyclic washing of above-mentioned acid treatment with deionized water, in 80～120 ℃ of drying 0.5 ~ 10 h, gets pretreated absorbent charcoal carrier;
⑶ infiltrate in advance 0.2～5 h with pretreated carried by active carbon body and function infiltrate, and the concentration of infiltrate is 0.1～2 mol/L, and the infiltrate quality is 0～4 with the ratio of quality of activated carbon, wherein, does not comprise 0 point;
⑷ be that the Pd source solution of 0.01～0.3 mol/L is added drop-wise in the absorbent charcoal carrier that infiltrates in advance lentamente with concentration, Pd is carried on the active carbon, namely obtain catalyst precarsor, wherein the quality of metal Pd adding is counted 1.0～5.0 wt.% by the catalyst gross mass;
⑸ adopt after drying method of reducing to process catalyst precarsor, namely obtains producing for the TMBQ hydrogenation Pd/C catalyst of TMHQ.
3. according to a kind of preparation method who produces the Pd/C catalyst of TMHQ for the TMBQ hydrogenation claimed in claim 2, the concentration that it is characterized in that acid solution used in described step ⑴ is 5 wt.%～10 wt.%.
4. according to a kind of preparation method who produces the Pd/C catalyst of TMHQ for the TMBQ hydrogenation claimed in claim 2, the granularity that it is characterized in that described carrier active carbon is 180～220 orders.
5. according to a kind of preparation method who produces the Pd/C catalyst of TMHQ for the TMBQ hydrogenation claimed in claim 2, it is characterized in that infiltrate used in step ⑶ is a kind of in sodium carbonate liquor or the oxalic acid solution.
6. according to a kind of preparation method who produces the Pd/C catalyst of TMHQ for the TMBQ hydrogenation claimed in claim 2, the Pd source that it is characterized in that Pd source solution used in step ⑷ is a kind of in acetate, nitrate, hydrochloride, the acid of chlorine palladium, palladium amine complex or the organic palladium of Pd.
7. according to a kind of preparation method who produces the Pd/C catalyst of TMHQ for the TMBQ hydrogenation claimed in claim 2, it is characterized in that method of reducing used in step ⑸ is a kind of in hydrogen reducing, formaldehyde reduction, reduction of ethylene glycol, formic acid reduction, the sodium formate reduction.
8. according to a kind of preparation method who produces the Pd/C catalyst of TMHQ for the TMBQ hydrogenation claimed in claim 3, it is characterized in that this preparation method comprises following concrete steps:
⑴ the acid treatment of carrier active carbon adds acid solution in the active carbon, and water-bath reflow treatment 2～4 h, acid solution adopt a kind of in hydrochloric acid, phosphoric acid or the salpeter solution, and the granularity of carrier active carbon is 180～220 orders;
⑵ extremely neutral with the active carbon cyclic washing of above-mentioned acid treatment with deionized water, in 80～120 ℃ of drying 0.5 ~ 10 h, gets pretreated absorbent charcoal carrier;
⑶ infiltrate in advance 0.2～5 h with pretreated carried by active carbon body and function infiltrate, the concentration of infiltrate is 0.1～2 mol/L, and the infiltrate quality is 0～4 with the ratio of quality of activated carbon, wherein, do not comprise 0 point, infiltrate adopts a kind of in sodium carbonate liquor or the oxalic acid solution;
⑷ be that the Pd source solution of 0.01～0.3 mol/L is added drop-wise in the absorbent charcoal carrier that infiltrates in advance lentamente with concentration, Pd is carried on the active carbon, namely obtain catalyst precarsor, wherein the quality that adds of metal Pd is counted 1.0～5.0 wt.% by the catalyst gross mass, and the Pd source of Pd source solution is a kind of in the acetate of Pd, nitrate, hydrochloride, the acid of chlorine palladium, palladium amine complex or the organic palladium;
⑸ adopt a kind of method of reducing in hydrogen reducing, formaldehyde reduction, reduction of ethylene glycol, formic acid reduction, the sodium formate reduction to process with catalyst precarsor after drying, namely obtains producing for the TMBQ hydrogenation Pd/C catalyst of TMHQ.
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