CN106732501A - A kind of preparation method of foam Pd/carbon catalyst - Google Patents
A kind of preparation method of foam Pd/carbon catalyst Download PDFInfo
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- CN106732501A CN106732501A CN201610952557.4A CN201610952557A CN106732501A CN 106732501 A CN106732501 A CN 106732501A CN 201610952557 A CN201610952557 A CN 201610952557A CN 106732501 A CN106732501 A CN 106732501A
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- foam
- carbon
- catalyst
- resinification
- preparation
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- 239000003054 catalyst Substances 0.000 title claims abstract description 64
- 239000006260 foam Substances 0.000 title claims abstract description 60
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 239000002028 Biomass Substances 0.000 claims abstract description 39
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 24
- 239000000084 colloidal system Substances 0.000 claims abstract description 12
- 239000011541 reaction mixture Substances 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 239000003960 organic solvent Substances 0.000 claims abstract description 11
- 238000005187 foaming Methods 0.000 claims abstract description 9
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 8
- 230000003197 catalytic effect Effects 0.000 claims abstract description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims abstract description 5
- 239000002184 metal Substances 0.000 claims abstract description 5
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims abstract description 5
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 238000005292 vacuum distillation Methods 0.000 claims description 10
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical group CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 8
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 6
- 230000004913 activation Effects 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 239000003863 metallic catalyst Substances 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 229920005830 Polyurethane Foam Polymers 0.000 claims description 4
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 4
- 239000004088 foaming agent Substances 0.000 claims description 4
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 4
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 4
- 229920000136 polysorbate Polymers 0.000 claims description 4
- 239000011496 polyurethane foam Substances 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- 239000003381 stabilizer Substances 0.000 claims description 4
- 239000004094 surface-active agent Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 239000002699 waste material Substances 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 2
- 150000001868 cobalt Chemical class 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- 150000002603 lanthanum Chemical class 0.000 claims description 2
- 150000002696 manganese Chemical class 0.000 claims description 2
- 150000002815 nickel Chemical class 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 claims description 2
- 229960001553 phloroglucinol Drugs 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 1
- 230000006837 decompression Effects 0.000 claims 1
- 239000003292 glue Substances 0.000 claims 1
- 159000000003 magnesium salts Chemical class 0.000 claims 1
- 238000001465 metallisation Methods 0.000 claims 1
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Substances CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 abstract description 11
- 238000000034 method Methods 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 6
- 229910000765 intermetallic Inorganic materials 0.000 abstract description 4
- 230000005484 gravity Effects 0.000 abstract description 3
- 241000219927 Eucalyptus Species 0.000 description 16
- 239000007833 carbon precursor Substances 0.000 description 16
- 239000000843 powder Substances 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000011347 resin Substances 0.000 description 12
- 229920005989 resin Polymers 0.000 description 12
- 239000002994 raw material Substances 0.000 description 11
- 235000019441 ethanol Nutrition 0.000 description 9
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 6
- 239000012685 metal catalyst precursor Substances 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 241000196324 Embryophyta Species 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 239000003610 charcoal Substances 0.000 description 3
- 210000004209 hair Anatomy 0.000 description 3
- VAOCPAMSLUNLGC-UHFFFAOYSA-N metronidazole Chemical compound CC1=NC=C([N+]([O-])=O)N1CCO VAOCPAMSLUNLGC-UHFFFAOYSA-N 0.000 description 3
- 229960000282 metronidazole Drugs 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 239000004872 foam stabilizing agent Substances 0.000 description 2
- 238000001802 infusion Methods 0.000 description 2
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical class Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910003978 SiClx Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- WQPDQJCBHQPNCZ-UHFFFAOYSA-N cyclohexa-2,4-dien-1-one Chemical compound O=C1CC=CC=C1 WQPDQJCBHQPNCZ-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000005909 ethyl alcohol group Chemical group 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 235000000396 iron Nutrition 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical class [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/084—Decomposition of carbon-containing compounds into carbon
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
-
- B01J35/60—
Abstract
The invention discloses a kind of preparation method of foam Pd/carbon catalyst, comprise the following steps：(1) pretreatment of abandoned biomass；(2) liquefaction of abandoned biomass；(3) resinification of liquefaction products, liquefaction products are in the presence of base catalyst, structure directing agent, add formaldehyde, there is macromolecular polymerization reaction with formaldehyde in liquefaction products, hydrochloric acid solution is added dropwise after reaction completely to be well mixed, add organic solvent to dissolve to form resinification reaction mixture, different type metallic compound is added in resinification reaction mixture as catalyst precursor, obtain resinification colloid；(4) template or certainly foaming method preparation Carbon foam catalyst precursor；(5) charing of Carbon foam catalyst precursor.The method of the present invention can prepare the Carbon foam metal catalytic material with difference in functionality.Prepared foam Pd/carbon catalyst has light specific gravity, and density is in 3.0g/cm3Hereinafter, and by simple technique the foam Pd/carbon catalyst of difference in functionality can be prepared.
Description
Technical field
The present invention relates to solid organic castoff resource and field of environment pollution control, and in particular to a kind of Carbon foam is urged
The preparation method of agent material.
Background technology
Carbon foam is a kind of light porous raw material of wood-charcoal of the tridimensional network that hole steep that wall steeped by hole and be connected with each other is constituted
Material, with light specific gravity, high surface area, high mechanical strength and chemically and thermally mechanics quality stable the features such as, it is often more important that, according to
The application target of prepared Carbon foam, adds appropriate related raw material, you can have to prepare in Carbon foam preparation process
The foam carbon material of specific function, the Carbon foam such as with catalysis and adsorption function.Can as needed be made simultaneously and appoint
The specification and shape of meaning are easy to use and reclaim.The carrier of traditional catalyst mainly includes aluminum oxide, silica gel, activated carbon, dioxy
SiClx, glass and some natural products such as float stone, diatomite etc., the preparation of catalyst are main using the side for impregnating or be coated with
Method.With the catalyst that these materials are prepared as carrier exist catalyst distribution it is uneven and load fastness it is not high, in catalyst
Coming off for supported catalyst is easily caused during use to cause the catalytic performance reduction of catalyst and causes the secondary of environment
Pollution.And metallic compound is added as the presoma of catalyst by the preparation process of Carbon foam, ultimately form foam
The complex that charcoal and catalyst are organically combined, can be prevented effectively from skewness and fastness of the catalyst on carrier relatively low
Shortcoming, can be widely applied to field of environment pollution control.
China produces forestry biomass discarded object, agricultural biomass discarded object and the water plant of considerable amount every year
Biomass the like waste, these biomass castoffs not only have that biomass is big, be distributed wide and reproducible feature, while it is changed
Point predominantly cellulose, half fiber and sugar etc. is studied containing carbohydrate.Therefore, being closed containing charing in these biomass castoffs
Thing provides abundant raw material as charcoal source to prepare Carbon foam catalyst carrier, not only reduces foam Pd/carbon catalyst
Manufacturing cost, while helping to open up the new way of biomass castoff resource, it is also possible to which reduction prepares foam high-area carbon pair
The demand of conventional petroleum and coal resources has important practical significance.
The information for being disclosed in the background section is merely intended to increase the understanding to general background of the invention, without answering
In being considered as recognizing or imply in any form that the information structure has been the prior art well known to persons skilled in the art.
The content of the invention
It is an object of the invention to provide a kind of preparation method of foam Pd/carbon catalyst, so as to solve traditional catalyst powder
End is difficult to reclaim, tack of the catalyst on carrier is poor, most metals and nonmetal catalyzed agent carrier are inhaled to target contaminant
A large amount of abandoned biomass that attached poor performance and China produce every year are badly in need of the problem of efficient resource technology.
To achieve the above object, the invention provides a kind of preparation method of foam Pd/carbon catalyst, comprise the following steps：
(1) pretreatment of abandoned biomass；
(2) liquefaction of abandoned biomass：In mass ratio it is 1 by step (1) pretreated abandoned biomass and liquefier:
The ratio mixing of 3-6, under the catalytic action of catalyst, is liquefied, and the liquefaction products are cooled into room temperature, is washed with methyl alcohol
Wash, through depressurizing, suction filtration obtains methyl alcohol-liquefied substance, then vacuum distillation removes methyl alcohol, obtains liquefaction products；
(3) resinification of liquefaction products：Liquefaction products obtained in the step (2) are in base catalyst, structure directing agent
Under effect, add formaldehyde, liquefaction products that macromolecular polymerization reaction occurs with formaldehyde, hydrochloric acid solution mixing is added dropwise after reaction completely equal
It is even, it is subsequently adding organic solvent and dissolves to form resinification reaction mixture, add metallic compound to make in resinification reaction mixture
It is the presoma of metallic catalyst, resinification colloid is obtained after being well mixed；
(4) prepared by Carbon foam catalyst precursor：Using template or from foaming；The template is in step (3)
In curing agent I is added in obtained resinification colloid, the template as Carbon foam skeleton will be used in the resin containing curing agent
Impregnate multiple in change colloid repeatedly, after volatilization removal organic solvent, obtain the precursor product of Carbon foam metallic catalyst；It is described
It is to be foamed certainly after foam stabilizer, foaming agent and curing agent II are added in obtained resinification colloid in step (3) from foaming, waves
After hair removal organic solvent, the precursor product of foam Pd/carbon catalyst is obtained；
(5) charing of Carbon foam metal catalyst precursor：Before Carbon foam metallic catalyst obtained in the step (4)
Drive body to be calcined, obtain foam Pd/carbon catalyst.
Preferably, in above-mentioned technical proposal, the pretreatment of abandoned biomass is in the step (1), by abandoned biomass
Cleaned, dried, then crushed；The abandoned biomass includes forestry abandoned biomass, agriculture waste biomass, aquatic plant
In thing abandoned biomass or daily life produce discarded paper in one or more.
Preferably, in above-mentioned technical proposal, the condensing temperature carried out in the step (2) is 140-180 DEG C, liquefying time
It is 1-3h.
Preferably, in above-mentioned technical proposal, the liquefier in the step (2) is phenol, catechol or phloroglucin
In one kind.
Preferably, in above-mentioned technical proposal, the catalyst in the step (2) is 85% phosphoric acid, the concentrated sulfuric acid or to benzene
One or several in sulfonic acid.
Preferably, in above-mentioned technical proposal, the structure directing agent in the step (3) is F127 and P123 surfactants
In one or more.
Preferably, in above-mentioned technical proposal, metallic compound is manganese salt, nickel salt, molysite, lanthanum salt, magnesium in the step (3)
One or more in salt, cobalt salt；Organic solvent is absolute ethyl alcohol in the step (3).
Preferably, in above-mentioned technical proposal, curing agent I described in the step (4) is hexamethylenetetramine；The template
Agent is polyurethane foam；The foam stabilizer is TWEEN Series surfactant；The foaming agent is pentane；The curing agent II
It is the concentrated sulfuric acid.
Preferably, in above-mentioned technical proposal, the preparation method of the Carbon foam metal catalyst precursor in the step (4)
For template or from foaming.
Preferably, in above-mentioned technical proposal, the removal organic solvent in the step (4) is absolute ethyl alcohol, at 60-80 DEG C
Lower evaporative removal organic solvent forms Carbon foam metal catalyst precursor.
Preferably, in above-mentioned technical proposal, the activation and charing of Carbon foam metal catalyst precursor in the step (5)
It is to calcine 1-4 hours obtained Carbon foam metal catalyst precursor for 500-800 DEG C under the atmosphere of nitrogen, obtains Carbon foam
Catalyst.
Compared with prior art, the present invention has the advantages that：
(1) present invention is with forestry biomass discarded object, agricultural biomass discarded object and water plant biomass castoff
Raw material prepares the carrier of Carbon foam metallic catalyst, can effectively solve the problems, such as that metallic catalyst carrier absorption property is poor.
(2) with forestry biomass discarded object, agricultural biomass discarded object and water plant biomass castoff as raw material, can
Conventional petroleum and Coal Chemical Industry intermediate are substituted as raw material synthetic foam Pd/carbon catalyst carrier using part, is efficiently solved above-mentioned
SOLID ORGANIC abandoned biomass deals with the problem of caused environmental pollution improperly, while being also the above-mentioned SOLID ORGANIC life of resource
Physical obsolescence thing provides new technical method.
(3) prepare Carbon foam metal catalyst precursor technology and combine by by liquefaction technology, Resin Technology, template
Get up, can with it is synthetically prepared go out homogeneous, the structurally ordered and porous Carbon foam Metal catalyst materials of size.By control
The key factor of each step, you can prepare the Carbon foam Metal catalyst materials with different catalysis.Institute of institute of the present invention
There are the method for offer raw material sources to be easy to get extensively, synthesis technique simple and be easily achieved.Prepared foam Pd/carbon catalyst tool
There is light specific gravity, density is in 3.0g/cm3Hereinafter, and by simple technique the foam Pd/carbon catalyst of difference in functionality can be prepared.
Brief description of the drawings
Fig. 1 is the Carbon foam catalyst preparation technology route map of proposition of the invention.
Specific embodiment
Below in conjunction with the accompanying drawings, specific embodiment of the invention is described in detail, it is to be understood that guarantor of the invention
Shield scope is not limited by specific embodiment.
Explicitly indicated that unless otherwise other, otherwise in entire disclosure and claims, term " including " or its change
Change such as "comprising" or " including " etc. and will be understood to comprise stated element or part, and do not exclude other units
Part or other parts.
Embodiment 1
Based on the preparation of Eucalyptus powder based foam carbon catalyst composite, comprise the following steps：
(1) pretreatment of abandoned biomass：The Eucalyptus that wood-working factory will be taken from considers the pre- places such as cleaned, dry and crushing to be worth doing
As raw material for standby after reason.
(2) liquefaction of Eucalyptus powder：Take the Eucalyptus powder after 5g is crushed to mix with 15g phenol, add the 0.5mL concentrated sulfuric acids (dense
98%) and 2mL phosphoric acid (concentration is 85%), the liquefaction reaction 2h at 160 DEG C spend for.Liquefaction products are cooled to room temperature, use methyl alcohol
Washing, through depressurizing, suction filtration obtains methyl alcohol-liquefied substance, and then vacuum distillation removes methyl alcohol at 50 DEG C in Rotary Evaporators, obtains liquid
Compound.
(3) resinification of liquefaction products：Gained liquefied substance is placed in there-necked flask, 1.25mol/L NaOH solutions are added
5mL.It is added dropwise at 60 DEG C after 37% formalin 25mL is finished and reacts 0.3h, continuously adds 0.2g structure directing agent F127, and
1.5h is reacted at 60 DEG C.It is continuously heating to 95 DEG C of reaction 1h.Resinification product is cooled to room temperature, adds 0.5mol/L HCL molten
Liquid 12.5mL is well mixed.After dissolving 1.6g manganese acetates and be added to and form homogeneous product in resinification product, it is in temperature
Moisture under 55 DEG C and vacuum 0.09Mpa in vacuum distillation removing resin.Rejoin 5mL anhydrous alcohol solutions removing moisture
Resinification product afterwards, obtains alcohol resin reaction mixture.
(4) preparation of foam carbon precursor：The hexamethylenetetramine 5g of ethanol dissolving is added in resinification reaction mixture,
Form final resinification colloid.Polyurethane foam is cut into the cube of size 10mm × 10mm × 10mm, by it repeatedly
It is impregnated into 3 times in the resinification colloid of gained, 60 DEG C of volatilization removal solvents obtain foam carbon precursor.
(5) activation and charing of foam carbon precursor：Foam carbon precursor is put into tube furnace, under nitrogen atmosphere,
500 DEG C are warmed up to 5 DEG C/min, 2h is carbonized, black foam Pd/carbon catalyst is obtained.
Embodiment 2
Based on the preparation of Eucalyptus powder based foam carbon catalyst composite, comprise the following steps：
(1) pretreatment of abandoned biomass：The Eucalyptus that wood-working factory will be taken from considers the pre- places such as cleaned, dry and crushing to be worth doing
As raw material for standby after reason.
(2) liquefaction of Eucalyptus powder：Take the Eucalyptus powder after 5g is crushed to mix with 15g phenol, add the 0.5mL concentrated sulfuric acids (dense
98%) and 2mL phosphoric acid (concentration is 85%), the liquefaction reaction 2h at 140 DEG C spend for.Liquefaction products are cooled to room temperature, use methyl alcohol
Washing, through depressurizing, suction filtration obtains methyl alcohol-liquefied substance, and then vacuum distillation removes methyl alcohol at 50 DEG C in Rotary Evaporators, obtains liquid
Compound.
(3) resinification of liquefaction products：Gained liquefied substance is placed in there-necked flask, 1.25mol/L NaOH solutions are added
5mL.It is added dropwise at 60 DEG C after 37% formalin 25mL is finished and reacts 0.3h, continuously adds 1.2g structure directing agent F127, and
1.5h is reacted at 60 DEG C.It is continuously heating to 95 DEG C of reaction 1h.Resinification product is cooled to room temperature, adds 0.5mol/L HCL molten
Liquid 12.5mL is well mixed.By 2.0g nitric acid dissolved ferric iron and after being added to and forming homogeneous product in resinification product, it is in temperature
Moisture under 55 DEG C and vacuum 0.09Mpa in vacuum distillation removing resin.Rejoin 5mL anhydrous alcohol solutions removing moisture
Resinification product afterwards, obtains alcohol resin reaction mixture.
(4) preparation of foam carbon precursor：The hexamethylenetetramine 5g of ethanol dissolving is added in resinification reaction mixture,
Form final resinification colloid.Polyurethane foam is cut into the cube of size 10mm × 10mm × 10mm, by it repeatedly
It is impregnated into 3 times in the resinification colloid of gained, 60 DEG C of volatilization removal solvents obtain foam carbon precursor.
(5) activation and charing of foam carbon precursor：Foam carbon precursor is put into tube furnace, under nitrogen atmosphere,
400 DEG C are warmed up to 5 DEG C/min, 2h is carbonized, black foam Pd/carbon catalyst is obtained.
Embodiment 3
Based on the preparation of Eucalyptus powder based foam carbon catalyst composite, comprise the following steps：
(1) pretreatment of abandoned biomass：The Eucalyptus that wood-working factory will be taken from considers the pre- places such as cleaned, dry and crushing to be worth doing
As raw material for standby after reason.
(2) liquefaction of Eucalyptus powder：Take the Eucalyptus powder after 5g is crushed to mix with 15g phenol, add the 0.5mL concentrated sulfuric acids (dense
98%) and 2mL phosphoric acid (concentration is 85%), the liquefaction reaction 2h at 160 DEG C spend for.Liquefaction products are cooled to room temperature, use methyl alcohol
Washing, through depressurizing, suction filtration obtains methyl alcohol-liquefied substance, and then vacuum distillation removes methyl alcohol at 50 DEG C in Rotary Evaporators, obtains liquid
Compound.
(3) resinification of liquefaction products：Gained liquefied substance is placed in there-necked flask, 1.25mol/L NaOH solutions are added
5mL.Be added dropwise at 60 DEG C after 37% formalin 25mL is finished and react 0.3h, continuously add 0.4g structure directing agents P123 and
F127, and react 1.5h at 60 DEG C.It is continuously heating to 95 DEG C of reaction 1h.Resinification product is cooled to room temperature, adds 0.5mol/
L HCL solution 12.5mL is well mixed.After dissolving 1.0g lanthanum chlorides and be added to and form homogeneous product in resinification product,
Temperature is 55 DEG C of moisture removed with vacuum distillation under vacuum 0.09Mpa in resin.5mL anhydrous alcohol solutions are rejoined to take off
Resinification product after moisture removal, obtains alcohol resin reaction mixture.
(4) preparation of foam carbon precursor：2mL foam stabilizers Tween 80,9mL hairs are sequentially added in alcohol resin product
The catalyst and the curing agent concentrated sulfuric acid of infusion pentane and 1.5mL, stirring mixing, are put into the mould of 100mm × 50mm × 50mm
In, 60 DEG C of foaming 1.0h are warming up to 80 DEG C of solidification 12h, obtain foam carbon precursor.
(5) activation and charing of foam carbon precursor：Foam carbon precursor is put into tube furnace, under nitrogen atmosphere,
600 DEG C are warmed up to 5 DEG C/min, 2h is carbonized, black foam Pd/carbon catalyst is obtained.
Embodiment 4
Based on the preparation of Eucalyptus powder based foam carbon catalyst composite, comprise the following steps：
(1) pretreatment of abandoned biomass：The Eucalyptus that wood-working factory will be taken from considers the pre- places such as cleaned, dry and crushing to be worth doing
As raw material for standby after reason.
(2) liquefaction of Eucalyptus powder：Take the Eucalyptus powder after 5g is crushed to mix with 15g phenol, add the 0.5mL concentrated sulfuric acids (dense
98%) and 2mL phosphoric acid (concentration is 85%), the liquefaction reaction 2h at 160 DEG C spend for.Liquefaction products are cooled to room temperature, use methyl alcohol
Washing, through depressurizing, suction filtration obtains methyl alcohol-liquefied substance, and then vacuum distillation removes methyl alcohol at 50 DEG C in Rotary Evaporators, obtains liquid
Compound.
(3) resinification of liquefaction products：Gained liquefied substance is placed in there-necked flask, 1.25mol/L NaOH solutions are added
5mL.It is added dropwise at 60 DEG C after 37% formalin 25mL is finished and reacts 0.3h, continuously adds 0.8g structure directing agent F127, and
1.5h is reacted at 60 DEG C.It is continuously heating to 95 DEG C of reaction 1h.Resinification product is cooled to room temperature, adds 0.5mol/L HCL molten
Liquid 12.5mL is well mixed.By 1.0g lanthanum chlorides and 2.0 nitric acid dissolved ferric irons and it is added to homogeneous product is formed in resinification product
Afterwards, the moisture under being 55 DEG C and vacuum 0.09Mpa in temperature in vacuum distillation removing resin.Rejoin 5mL absolute ethyl alcohols
Resinification product after dissolving removing moisture, obtains alcohol resin reaction mixture.
(4) preparation of foam carbon precursor：2mL foam stabilizers Tween 80,9mL hairs are sequentially added in alcohol resin product
The catalyst and the curing agent concentrated sulfuric acid of infusion pentane and 1.5mL, stirring mixing, are put into the mould of 100mm × 50mm × 50mm
In, 60 DEG C of foaming 1.0h are warming up to 80 DEG C of solidification 12h, obtain foam carbon precursor.
(5) activation and charing of foam carbon precursor：Foam carbon precursor is put into tube furnace, under nitrogen atmosphere,
600 DEG C are warmed up to 5 DEG C/min, 2h is carbonized, black foam Pd/carbon catalyst is obtained.
Embodiment 5
The test of the raw element agent metronidazole catalytic degradation effect of foam Pd/carbon catalyst confrontation
Degradation condition：The initial concentration 10mg/L of metronidazole, the Carbon foam catalyst amount 2g/L in embodiment 4, system
30 DEG C of temperature, natural pH.The ozone catalytic for continuing to be passed through concentration 50ppm according to the speed of 2L/min in solution system is degraded
2h, metronidazole clearance can reach 90%.
Embodiment 6
Test of the foam Pd/carbon catalyst to volatile organic matter dimethylbenzene degradation effect
Degradation condition：Carbon foam catalyst amount 30g in embodiment 1 is filled in 50mL fixed bed reactors, is controlled
The inlet gas concentration 2ppm of dimethylbenzene processed, 30 DEG C of environment temperature.Continue to be passed through according to the speed of 2L/min in fixed bed reactors
The ozone catalytic degraded 2h of concentration 50ppm, dimethylbenzene clearance can reach 90%.
The foregoing description to specific illustrative embodiment of the invention be in order to illustrate and illustration purpose.These descriptions
It is not wishing to limit the invention to disclosed precise forms, and it will be apparent that according to above-mentioned teaching, can be much changed
And change.The purpose of selecting and describing the exemplary embodiment is that explaining that certain principles of the invention and its reality should
With so that those skilled in the art can realize and using a variety of exemplaries of the invention and
A variety of selections and change.The scope of the present invention is intended to be limited by claims and its equivalents.
Claims (10)
1. a kind of preparation method of foam Pd/carbon catalyst, it is characterised in that comprise the following steps：
(1) pretreatment of abandoned biomass；
(2) liquefaction of abandoned biomass：In mass ratio it is 1 by step (1) pretreated abandoned biomass and liquefier:3-6
Ratio mixing, under the catalytic action of catalyst, liquefied, the liquefaction products are cooled to room temperature, wash with methyl alcohol, warp
Decompression suction filtration obtains methyl alcohol-liquefied substance, and then vacuum distillation removes methyl alcohol, obtains liquefaction products；
(3) resinification of liquefaction products：Liquefaction products are in base catalyst, the effect of structure directing agent obtained in the step (2)
Under, add formaldehyde, liquefaction products that macromolecular polymerization reaction occurs with formaldehyde, hydrochloric acid solution is added dropwise after reaction completely and is well mixed,
It is subsequently adding organic solvent to dissolve to form resinification reaction mixture, different types of metallization is added in resinification reaction mixture
Compound is well mixed and obtains resinification colloid as the presoma of metallic catalyst；
(4) prepared by Carbon foam catalyst precursor：Using template or from foaming；The template is the system in step (3)
Curing agent I is added in the resinification colloid for obtaining, the template as Carbon foam skeleton will be used in the resinification glue containing curing agent
Impregnate multiple in body repeatedly, after volatilization removal organic solvent, obtain the precursor product of foam Pd/carbon catalyst；It is described from foaming
It is have from foaming, volatilization removal after adding foam stabilizer, foaming agent and curing agent II in obtained resinification colloid in step (3)
After machine solvent, the precursor product of foam Pd/carbon catalyst is obtained；
(5) charing of Carbon foam catalyst precursor：Carbon foam catalyst precursor obtained in the step (4) is forged
Burn, obtain foam Pd/carbon catalyst.
2. the preparation method of foam Pd/carbon catalyst according to claim 1, it is characterised in that discarded in the step (1)
The pretreatment of biomass is to clean abandoned biomass, dry, and is then crushed；The abandoned biomass is useless including forestry
The one kind abandoned in the discarded paper produced in biomass, agriculture waste biomass, water plant abandoned biomass or daily life
Or it is several.
3. the preparation method of foam Pd/carbon catalyst according to claim 1, it is characterised in that carried out in the step (2)
Condensing temperature be 140-180 DEG C, liquefying time is 1-3h.
4. the preparation method of foam Pd/carbon catalyst according to claim 1, it is characterised in that the liquid in the step (2)
Agent is the one kind in phenol, catechol or phloroglucin.
5. the preparation method of foam Pd/carbon catalyst according to claim 1, it is characterised in that urging in the step (2)
Agent is one or several in 85% phosphoric acid, the concentrated sulfuric acid or P-TOLUENE SULFO ACID 99.
6. the preparation method of foam Pd/carbon catalyst according to claim 1, it is characterised in that the knot in the step (3)
Structure directed agents are one or more in F127 and P123 surfactants.
7. the preparation method of foam Pd/carbon catalyst according to claim 1, it is characterised in that metal in the step (3)
Compound be manganese salt, nickel salt, molysite, lanthanum salt, magnesium salts, cobalt salt in one or more.
8. the preparation method of foam Pd/carbon catalyst according to claim 1, it is characterised in that described in the step (4)
Curing agent I is hexamethylenetetramine；The template is polyurethane foam；The foam stabilizer is TWEEN Series surfactant；
The foaming agent is pentane；The curing agent II is the concentrated sulfuric acid.
9. the preparation method of foam Pd/carbon catalyst according to claim 1, it is characterised in that going in the step (4)
Except organic solvent is absolute ethyl alcohol, evaporative removal organic solvent forms Carbon foam catalyst precursor at 60-80 DEG C.
10. the preparation method of foam Pd/carbon catalyst according to claim 1, it is characterised in that foam in the step (5)
The activation and charing of Pd/carbon catalyst presoma are calcined 1-4 hours for 500-800 DEG C under the atmosphere of nitrogen, obtain Carbon foam catalysis
Agent.
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| CN113385163A (en) * | 2021-06-16 | 2021-09-14 | 西南林业大学 | Foam carbon heterogeneous solid base catalyst for grease transesterification and preparation method thereof |
| CN115501864A (en) * | 2022-10-26 | 2022-12-23 | 广州欣旺科技有限公司 | Biomass porous adsorbent for waste gas treatment and preparation method thereof |
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