CN106853371A - A kind of preparation method and application of biomass carbon base Fe-series catalyst - Google Patents
A kind of preparation method and application of biomass carbon base Fe-series catalyst Download PDFInfo
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- CN106853371A CN106853371A CN201611128883.XA CN201611128883A CN106853371A CN 106853371 A CN106853371 A CN 106853371A CN 201611128883 A CN201611128883 A CN 201611128883A CN 106853371 A CN106853371 A CN 106853371A
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- biomass carbon
- carbon base
- series catalyst
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- lignin
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- 239000003054 catalyst Substances 0.000 title claims abstract description 97
- 239000002028 Biomass Substances 0.000 title claims abstract description 74
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 125
- 238000007747 plating Methods 0.000 claims abstract description 57
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 56
- 239000000243 solution Substances 0.000 claims abstract description 54
- 239000000126 substance Substances 0.000 claims abstract description 54
- 239000002699 waste material Substances 0.000 claims abstract description 49
- 229920005610 lignin Polymers 0.000 claims abstract description 38
- 102000008186 Collagen Human genes 0.000 claims abstract description 35
- 108010035532 Collagen Proteins 0.000 claims abstract description 35
- 229920001436 collagen Polymers 0.000 claims abstract description 35
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 14
- 238000001291 vacuum drying Methods 0.000 claims abstract description 13
- 239000007864 aqueous solution Substances 0.000 claims abstract description 11
- 238000000227 grinding Methods 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 238000010792 warming Methods 0.000 claims abstract description 9
- 150000002978 peroxides Chemical class 0.000 claims abstract description 8
- 230000001590 oxidative effect Effects 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract 2
- 238000000034 method Methods 0.000 claims description 31
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 16
- 230000008569 process Effects 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 12
- 229910052742 iron Inorganic materials 0.000 claims description 11
- 238000009413 insulation Methods 0.000 claims description 8
- 229910001453 nickel ion Inorganic materials 0.000 claims description 8
- 238000001556 precipitation Methods 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 8
- 239000006228 supernatant Substances 0.000 claims description 8
- 238000007306 functionalization reaction Methods 0.000 claims description 7
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- 239000012670 alkaline solution Substances 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 210000000988 bone and bone Anatomy 0.000 claims description 2
- 239000011121 hardwood Substances 0.000 claims description 2
- 238000007873 sieving Methods 0.000 claims description 2
- 244000144972 livestock Species 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 16
- 230000003197 catalytic effect Effects 0.000 abstract description 16
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 8
- 230000000593 degrading effect Effects 0.000 abstract description 3
- 239000011148 porous material Substances 0.000 abstract description 3
- 230000001681 protective effect Effects 0.000 abstract description 2
- 238000007254 oxidation reaction Methods 0.000 description 19
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 239000002351 wastewater Substances 0.000 description 17
- 230000003647 oxidation Effects 0.000 description 16
- 230000006872 improvement Effects 0.000 description 13
- 239000002808 molecular sieve Substances 0.000 description 11
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 9
- 230000009471 action Effects 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- SPIFDSWFDKNERT-UHFFFAOYSA-N nickel;hydrate Chemical compound O.[Ni] SPIFDSWFDKNERT-UHFFFAOYSA-N 0.000 description 6
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 5
- 239000012298 atmosphere Substances 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 4
- 235000011613 Pinus brutia Nutrition 0.000 description 4
- 241000018646 Pinus brutia Species 0.000 description 4
- 238000007605 air drying Methods 0.000 description 4
- 239000002910 solid waste Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000002779 inactivation Effects 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- -1 percolate Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000012018 catalyst precursor Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000010525 oxidative degradation reaction Methods 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 229910001867 inorganic solvent Inorganic materials 0.000 description 1
- 239000003049 inorganic solvent Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000010977 jade Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000010914 pesticide waste Substances 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000012460 protein solution Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000009279 wet oxidation 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
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention provides a kind of preparation method and application of biomass carbon base Fe-series catalyst, the preparation method of the biomass carbon base Fe-series catalyst is comprised the following steps：Collagen aqueous solution is first prepared, lignin is added, and adds inorganic molysite solution, 20 ~ 60 min are aged after blending homogeneous；Then vacuum drying is ground and obtains grinding product to constant weight；By the grinding product under nitrogen protective condition, 400 1000 DEG C are warming up to, are incubated natural cooling after 14 h, then be ground, obtain biomass carbon base Fe-series catalyst sample.Catalyst of the invention has specific surface area and good pore structure higher, its active component is highly combined with catalyst carrier, can with efficient catalytic wet-type peroxide oxidizing degrading high concentration chemical nickel plating waste solution, with stability it is strong, reusing is high the characteristics of.
Description
Technical field
The present invention relates to a kind of preparation method and application of heterogeneous catalysis, more particularly to a kind of biomass carbon base iron system
The preparation method and application of catalyst.
Background technology
For high concentration complex state nickel present in chemical nickel plating waste solution, conventional oxidation agent for example hydrogen peroxide, potassium permanganate,
The direct addition of sodium hypochlorite, ozone etc. and the utilization of chemical precipitation method cannot realize its efficient removal, in the urgent need to propose or
Set up new green, efficient, economic improvement principle and technology.
Catalytic wet hydrogen peroxide oxidation technology (Catalytic wet peroxide oxidation, CWPO) be with
Based on conventional catalyst wet oxidation and Fenton oxidation technology, by the advanced oxidation skill of catalyst inducement oxidation reaction
Art, it is dirty that it is generally applicable to the concentration environment high such as phenol wastewater, waste water from dyestuff, percolate, pesticide waste water, pharmacy waste water
Contaminate degraded and the mineralising of thing.In view of the technology can provide or construct a class special efficient oxidation reaction environment, strengthen hydroxyl
Free radical is expected to fundamentally solve chemical nickel plating waste solution traditional treatment method contact break effect to the efficient degradation of target contaminant
The problem such as really poor, oxidation efficiency is low, sludge yield is high.
In CWPO technologies, the selection of catalyst is the key for implementing efficient degradation.Early stage is studied main using soluble
Transition metal salt material as homogeneous catalyst, to realize the oxidation catalysis of molecule or ion aspect, although such catalyst
Reactivity is high, selectivity is strong, but pH value in reaction condition is harsh, and follow-up phase needs extra separation and Treatment of Sludge ring
, easily there is secondary pollution in section.Therefore, research emphasis at this stage focus primarily upon it is heterogeneous as noble metal, transition metal,
In the research and development of rare earth metal catalyst.
For transition metal series catalysts, traditional preparation methods are that catalyst carrier material and active component are carried out into two
Secondary assembling, is loaded by way of dipping-roasting, although simple to operate, is conducive to the large-scale production of catalyst, only
Surface deposition or selective aperture deposition of the active component in catalyst carrier can be realized, it is impossible to ensure active component and carrier
Highly combine；Meanwhile, by solution acid-base condition, oxidation reaction process, active component crystal structure, catalyst surface carbon distribution behavior
Etc. factor influence, there is loss of active component, catalytic performance inactivation, stability in such catalyst all the time during long-term use
The problems such as forfeiture.
Lignin is the second largest natural polymerses that cellulose is quantitatively only second in nature.As industry
The byproduct of pulp manufacture and biorefinery ethanol, its practical efficiency only less than 10 %, finds new recycling approach
Have become the focus of lignin industrial development.It is former based on lignin and its derivative in solid catalyst application field
Material, the catalyst prepared after modified such as organic/inorganic solvent dipping, semi-annular jade pendant, carbonization or high temperature oxidation process, in biological bavin
Oil production, chemical reagent synthesis field show efficient catalytic performance and the universality to different type reaction, but are related to it
The research of CWO treatment high concentration plating wastewater is rarely reported.
The content of the invention
For above technical problem, the invention discloses a kind of biomass carbon base Fe-series catalyst preparation method and should
Not only can effectively suppress the molten of iron system active component in Oxidative Degradation Process with, the biomass carbon base Fe-series catalyst for obtaining
Go out, and can be strong, repeatedly sharp with stability with efficient catalytic wet-type peroxide oxidizing degrading high concentration chemical nickel plating waste solution
With property it is high the characteristics of.
In this regard, the technical solution adopted by the present invention is：
A kind of preparation method of biomass carbon base Fe-series catalyst, it is comprised the following steps：
Step S1：Prepare collagen aqueous solution；
Step S2：Lignin is added in the collagen aqueous solution, and adds inorganic molysite solution, be aged after blending homogeneous
20~60 min；Then vacuum drying is ground and obtains grinding product to constant weight；
Step S3：By the grinding product under the conditions of inert gas shielding, it is warming up to the rate of heat addition of 1-10 DEG C/min
400-1000 DEG C, room temperature is naturally cooled to after insulation 1-4 h, then be ground, obtain biomass carbon base Fe-series catalyst sample
Product；The inert gas is preferably nitrogen.
As a further improvement on the present invention, it also includes step S4：The sample is washed in alkaline solution, then
It is washed with deionized to neutrality, the biomass carbon base Fe-series catalyst of functionalization is obtained after heating, drying.
Research finds, armaticity carbon source material is introduced in lignin system and is conducive to constructing high intensity in pyrolysis phase many
Ring structure, assigns system stronger adhesive property, improves the mechanical strength of its carbonized product.This technical scheme is common using raw material
Biomass carbon base Fe-series catalyst prepared by mixed, fixed-type, high temperature cracking method has specific surface area higher and good
Pore structure, its active component is distributed in catalyst surface and inside the diversified forms such as to cover, embed, embed, with catalyst
Carrier height is combined.The technology is not only expected to solve traditional catalyst loss of active component, catalytic during long-term use
The problems such as energy inactivation, loss of stability；And wet-type peroxide oxidizing technique can be realized to high concentration chemical nickel plating waste solution
Efficient degradation；It is also beneficial to expand lignin, collagen biomass solid wastes simultaneously in Treatment of Industrial Water field
Higher value application.
As a further improvement on the present invention, volume of the iron system active component on carrier is 5-40 wt%, described
The quality of carrier is the quality of collagen and the quality sum of lignin.Wherein, iron system active component is on carrier
Volume is the quality and collagen and the ratio of lignin quality sum of ferro element.The quality and inorganic molysite of i.e. described carrier
In the mass ratio of iron that contains be 1：（0.050~0.4）.
Preferably, collagen is with the mass ratio of lignin in the carrier（1~9）：（1~9）.
As a further improvement on the present invention, in step S2, contain in the collagen, lignin and inorganic molysite
The ratio between the mass fraction of iron be 1：3：（0.2~1.6）.
As a further improvement on the present invention, in step S1, collagen is placed in distilled water, in 60-70 DEG C of condition
Lower stirring and dissolving obtains collagen aqueous solution.
As a further improvement on the present invention, in step S2, the advanced sector-style of lignin is dry, break process, and vacuum
Drying is used to constant weight after grinding sieving.
As a further improvement on the present invention, the temperature that the lignin carries out vacuum drying is 40-50 DEG C；Step S4
In, the OH of alkaline solution-Concentration is 0.1 ~ 0.2 mol/L.
As a further improvement on the present invention, the preparation method of the biomass carbon base Fe-series catalyst includes following step
Suddenly：
（1）Lignin is air-dried, break process, and under the conditions of 40-50 DEG C vacuum drying to constant weight, ground 100 mesh
Sieve；
（2）1-9 g collagens are placed in 15 mL distilled water, stirring and dissolving forms collagen under the conditions of 60-70 DEG C of temperature
Protein solution；Add step（1）In lignin powder 1-9 g, be slowly added dropwise 1.79-14.29 under lasting stirring action
Mol/L inorganic molysites（In terms of elemental iron）The mL of solution 5；It is placed under the conditions of 20-25 DEG C of room temperature after blending homogeneous and is aged 30
min；Vacuum drying is to constant weight under being subsequently placed in 60-70 DEG C of atmosphere of temperature, ground 100 mesh sieve；
（3）By step（2）The grinding product of middle acquisition is placed in tube type vacuum atmospheric resistance furnace, under nitrogen protective condition, with
The rate of heat addition of 1-10 DEG C/min is warming up to 400-1000 DEG C, and room temperature, ground mistake 100 are naturally cooled to after insulation 1-4 h
Mesh sieve；
（4）By step（3）The sample of middle acquisition is in OH-Concentration for 0.1-0.2 mol/L dilute alkaline soln in wash 20-30
min；Then ion-cleaning to neutrality is spent, the biomass carbon base Fe-series catalyst of functionalization can be obtained after heating, drying.
As a further improvement on the present invention, the lignin is at least one of hardwood quality or soi lwood lignin.
As a further improvement on the present invention, described collagen sources are in biomass solid wastes.
As a further improvement on the present invention, the collagen sources are dynamic in pigskin, ox bone, tanning leftover or aquatic products
Thing.
As a further improvement on the present invention, described inorganic molysite is at least one in iron chloride or ferric nitrate.
The invention also discloses a kind of application of biomass carbon base Fe-series catalyst, the biomass carbon base Fe-series catalyst
Prepared using the preparation method of the biomass carbon base Fe-series catalyst described in as above any one, it is applied in catalytic wet
In hydrogen peroxide oxidation degraded chemical nickel plating waste solution.
As a further improvement on the present invention, the application of the biomass carbon base Fe-series catalyst is comprised the following steps：
Step A：The pH value of presetting chemical nickel plating waste solution is added to chemical plating the biomass carbon base Fe-series catalyst to 3-8
In nickel waste liquid, stir and evenly mix and obtain mixed system, the input amount of the biomass carbon base Fe-series catalyst is every liter of chemical nickel plating
Waste liquid puts into 10 ~ 50g；
Step B：To adding H in the mixed system2O2Solution, reacts 20-30 min under stirring；Wherein, the H2O2Press
It is 3.33 ~ 16.65g according to every liter of chemical nickel plating waste solution addition；
Step C：Alkaline solution is subsequently adding, to 9-11, precipitation is centrifuged regulation pH value after stirring, takes supernatant and determines nickel
Ion concentration.
Preferably, the biomass carbon base Fe-series catalyst for being prepared using the above method is dropped in catalytic wet hydrogen peroxide oxidation
Application in solution high concentration chemical nickel plating waste solution, including：
（1）1-5 g biomass carbon base Fe-series catalysts are added into 100 mL chemical nickel plating waste solutions, is stirred and evenly mixed, it is described
The original water quality characteristic of chemical nickel plating waste solution is COD 45000-50000 mg/L, Ni2+ 4700 mg/L, Cu2+ 100 mg/L,
pH 5.3.Reaction starts preceding presetting its pH value to 3-8, and stir speed (S.S.) is 700 rpm；
（2）It is continuous that 1-5 mL H are added dropwise2O2（30 wt%）Solution is to step（1）In mixed system in, under stirring react
20-30 min；
（3）Reaction adds 1-10 mol/L NaOH solutions, regulation pH value to be stirred under the conditions of the rpm of speed 150 to 9-11 after terminating
15 min are mixed, precipitation is separated after centrifugal action, take supernatant and determine nickel ion concentration.
Compared with prior art, beneficial effects of the present invention are：
First, technical scheme raw material, inorganic molysite based on lignin, collagen biomass solid wastes
It is active component presoma, by the technique such as intimate blending, fixed-type, high temperature pyrolysis, building has ad hoc structure and function
Catalyst system, it has specific surface area and a good pore structure higher, and its active component is covering, embed, embed
Catalyst surface and inside are distributed in etc. diversified forms, are highly combined with catalyst carrier.
Second, technical scheme not only solves traditional catalyst activearm shunting during long-term use
The problems such as mistake, catalytic performance inactivation, loss of stability；And wet-type peroxide oxidizing technique can be realized to high concentration chemistry
The efficient degradation of nickel-plating waste liquid；It is also beneficial to expand lignin simultaneously, collagen biomass solid wastes are at industry water
The higher value application in reason field.
3rd, the biomass carbon base Fe-series catalyst obtained by the present invention not only can effectively suppress in Oxidative Degradation Process
The dissolution of iron system active component, and can have with efficient catalytic wet-type peroxide oxidizing degrading high concentration chemical nickel plating waste solution
There is the characteristics of stability is strong, reusing is high.
Brief description of the drawings
Fig. 1 is the biomass carbon base Fe-series catalyst treatment high concentration chemical plating of the % volumes of use 40 that embodiment 1 is provided
Nickel waste water nickel concentration changes over time situation map.
Fig. 2 is the biomass carbon base Fe-series catalyst treatment high concentration chemical plating of the % volumes of use 40 that embodiment 1 is provided
Nickel waste water nickel clearance changes over time situation map.
Fig. 3 be embodiment 2 provide use ironloading molecular sieves catalyst treatment high concentration chemical nickle-plating wastewater nickel concentration with
Time change situation map.
Fig. 4 is the use ironloading molecular sieves catalyst treatment high concentration chemical nickle-plating wastewater nickel clearance that embodiment 2 is provided
Change over time situation map.
Fig. 5 is the biomass carbon base Fe-series catalyst treatment high concentration chemical nickel plating of the % volumes of use 5 that embodiment 3 is provided
Nickel-containing wastewater concentration changes with time situation map.
Fig. 6 is the biomass carbon base Fe-series catalyst treatment high concentration chemical nickel plating of the % volumes of use 5 that embodiment 3 is provided
Nickel-containing wastewater clearance changes over time situation map.
Fig. 7 is the biomass carbon base Fe-series catalyst treatment high concentration chemical plating of the % volumes of use 20 that embodiment 4 is provided
Nickel waste water nickel concentration changes over time situation map.
Fig. 8 is the biomass carbon base Fe-series catalyst treatment high concentration chemical plating of the % volumes of use 20 that embodiment 4 is provided
Nickel waste water nickel clearance changes over time situation map.
Fig. 9 is the biomass carbon base Fe-series catalyst treatment high concentration chemical plating of the % volumes of use 40 that embodiment 5 is provided
Nickel waste water nickel concentration changes over time situation map, wherein, the presetting chemical nickel plating waste solution pH value of high concentration chemical nickle-plating wastewater
To 8.
Figure 10 is the biomass carbon base Fe-series catalyst treatment high concentration chemical plating of the % volumes of use 40 that embodiment 5 is provided
Nickel waste water nickel clearance changes over time situation map, wherein, the presetting chemical nickel plating waste solution pH of high concentration chemical nickle-plating wastewater
It is worth to 8.
Specific embodiment
Below in conjunction with the accompanying drawings, preferably embodiment of the invention is described in further detail.
Embodiment 1
First, biomass carbon base Fe-series catalyst is prepared
The preparation method of biomass carbon base Fe-series catalyst, comprises the following steps that：
（1）After air-drying pine lignin is size-reduced, ground 100 mesh sieve after 40-50 DEG C of drying of low temperature；
（2）Weigh 2.5 g collagens to be placed in 15 mL water, collagen aqueous solution is formed in heating for dissolving at 65 DEG C, and
7.5 g lignin are added, the wherein mass ratio of collagen and lignin is 1:3, it is slow to said mixture in whipping process
The mL of ferric chloride solution 5 of 14.29 mol/L is added dropwise, it is 40 % that the volume of wherein iron chloride is calculated in mass percent；Blending homogeneous
After be placed under the conditions of 20-25 DEG C of room temperature and be aged 30 min；Vacuum drying obtains to constant weight under being subsequently placed in 60 DEG C of atmosphere of temperature
Obtain biomass carbon base Fe-series catalyst presoma, ground 100 mesh sieve；
（3）Above-mentioned biomass carbon base Fe-series catalyst presoma is positioned in tube type vacuum atmospheric resistance furnace, in nitrogen protection
Under, 800 DEG C are warming up to the rate of heat addition of 1 DEG C/min, naturally cool to room temperature, ground 100 mesh sieve after 1 h of insulation；
（4）By step（3）The sample of middle acquisition is in OH-Concentration be 0.1 mol/L dilute alkaline soln in wash 30 min;Then
Ion-cleaning to neutrality is spent, the biomass carbon base Fe-series catalyst of functionalization can be obtained after heating, drying.
2nd, catalytic wet hydrogen peroxide oxidation high concentration chemical nickel plating waste solution
High concentration chemical nickel plating waste solution is mainly derived from Shenzhen industrial park board production enterprise, and its water quality characteristic is：
COD 45000-50000 mg/L, Ni2+4700 mg/L, Cu2+100 mg/L, pH 5.3.
Specific method for treating waste liquid, it is as follows：
（1）Presetting chemical nickel plating waste solution pH value is added to 100 mL chemical platings 3 g biomass carbon base Fe-series catalysts to after 3
In nickel waste liquid, stirred and evenly mixed under the conditions of the rpm of speed 700；
（2）It is continuous that 3 mL H are added dropwise2O2（30 wt%）Into above-mentioned mixed system, 120 min are reacted under stirring；
（3）Reaction adjusts pH value to 9-11 after terminating by 1 mol/L NaOH solutions, is stirred under the conditions of the rpm of speed 150
15 min, precipitation is separated after centrifugal action, is taken supernatant and is determined nickel ion concentration.
As depicted in figs. 1 and 2, the water outlet Ni after above method treatment2+Concentration is down to 409 mg/L by 1052 mg/L, goes
Except rate is up to 61.2 %.
Embodiment 2
First, ironloading molecular sieves catalyst is prepared
From ZSM-5 molecular sieve as carrier, wherein molecular sieve silica alumina ratio is 50, and aperture is 0.5, relative crystallinity >=95
%, specific surface area >=320 m2/g.Using excessive infusion process load active component iron, comprise the following steps that：
（1）ZSM-5 molecular sieve carries out 40-50 DEG C of drying pretreatment of low temperature；
（2）Under 65 DEG C of constant temperatures, the ZSM-5 molecular sieve of drying is put into a certain amount of ferric chloride solution and is stirred and evenly mixed,
It is 40 % that the volume of wherein iron chloride is calculated in mass percent；After stirring is homogeneous, 100 DEG C of electric drying oven with forced convection temperature is placed in
To constant weight, ground 100 mesh sieve obtains ironloading molecular sieves catalyst precursor for drying；
（3）Above-mentioned catalyst precursor is placed in tube type vacuum atmospheric resistance furnace, under nitrogen protection, with adding for 1 DEG C/min
Hot speed is warming up to 800 DEG C, and room temperature, ground 100 mesh sieve are naturally cooled to after 1 h of insulation；
（4）By step（3）The sample of middle acquisition is washed with deionized to neutrality, and ironloading molecular sieves can be obtained after heating, drying
Catalyst.
2nd, catalytic wet hydrogen peroxide oxidation high concentration chemical nickel plating waste solution
Identical with being disposed waste liquid in embodiment 1, high concentration chemical nickel plating waste solution is mainly derived from Shenzhen industrial park circuit
Plate manufacturing enterprise, its water quality characteristic is：COD 45000-50000 mg/L, Ni2+4700 mg/L, Cu2+100 mg/L, pH
5.3。
Specific method for treating waste liquid, it is as follows：
（1）3 g ironloading molecular sieves catalyst are added to 100 mL chemical nickel platings and given up by presetting chemical nickel plating waste solution pH value to after 3
In liquid, stirred and evenly mixed under the conditions of the rpm of speed 700；
（2）It is continuous that 3 mL H are added dropwise2O2（30 wt%）Into above-mentioned mixed system, 120 min are reacted under stirring；
（3）Reaction adjusts pH value to 9-11 after terminating by 1 mol/L NaOH solutions, is stirred under the conditions of the rpm of speed 150
15 min, precipitation is separated after centrifugal action, is taken supernatant and is determined nickel ion concentration.
As shown in Figure 3 and Figure 4, the water outlet Ni after above method treatment2+Concentration is down to 949 mg/L by 1090 mg/L, goes
Except rate up to 12.9%.
By embodiment 1 compared with the ironloading molecular sieves catalyst treatment effect of embodiment 2, biomass carbon base is answered in embodiment 1
Oxidation contact break effect is significant of the Fe-series catalyst to high concentration nickel-plating waste water is closed, the clearance of nickel improves 48.3% in waste liquid, in fact
Efficient degradation of the existing wet-type peroxide oxidizing technique to high concentration chemical nickel plating waste solution.
Embodiment 3
First, the preparation method of the compound Fe-series catalyst of biomass carbon base, comprises the following steps that：
（1）After air-drying pine lignin is size-reduced, ground 100 mesh sieve after 40-50 DEG C of drying of low temperature；
（2）Weigh 2.5 g collagens to be placed in 15 mL water, collagen aqueous solution is formed in heating for dissolving at 65 DEG C, and
7.5 g lignin are added, the wherein mass ratio of collagen and lignin is 1:3, it is slow to said mixture in whipping process
The mL of ferric chloride solution 5 of 1.79 mol/L is added dropwise, it is 5 % that the volume of wherein iron chloride is calculated in mass percent；After blending homogeneous
It is placed under the conditions of 20-25 DEG C of room temperature and is aged 40 min；Vacuum drying obtains to constant weight under being subsequently placed in 70 DEG C of atmosphere of temperature
Biomass carbon base Fe-series catalyst presoma, ground 100 mesh sieve；
（3）Above-mentioned biomass carbon base Fe-series catalyst presoma is positioned in tube type vacuum atmospheric resistance furnace, in nitrogen protection
Under, 1000 DEG C are warming up to the rate of heat addition of 10 DEG C/min, naturally cool to room temperature, ground 100 mesh sieve after 1 h of insulation；
（4）By step（3）The sample of middle acquisition is in OH-Concentration be 0.1 mol/L dilute alkaline soln in wash 30 min;Then
Ion-cleaning to neutrality is spent, the biomass carbon base Fe-series catalyst of functionalization can be obtained after heating, drying.
2nd, catalytic wet hydrogen peroxide oxidation high concentration chemical nickel plating waste solution
High concentration chemical nickel plating waste solution is mainly derived from Shenzhen industrial park board production enterprise, and its water quality characteristic is：
COD 45000-50000 mg/L, Ni2+ 4700 mg/L, Cu2+ 100 mg/L, pH 5.3。
Specific method for treating waste liquid, it is as follows：
（1）Presetting chemical nickel plating waste solution pH value is added to 100 mL chemical platings 3 g biomass carbon base Fe-series catalysts to after 3
In nickel waste liquid, stirred and evenly mixed under the conditions of the rpm of speed 700；
（2）It is continuous that 3 mL H are added dropwise2O2（30 wt%）Into above-mentioned mixed system, 120 min are reacted under stirring；
（3）Reaction adjusts pH value to 9-11 after terminating by 1 mol/L NaOH solutions, is stirred under the conditions of the rpm of speed 150
15 min, precipitation is separated after centrifugal action, is taken supernatant and is determined nickel ion concentration.
As shown in Figure 5 and Figure 6, the water outlet Ni after above method treatment2+Concentration is down to 900 mg/L by 1091 mg/L, goes
Except rate up to 17.5 %.
Embodiment 4
First, the preparation method of the compound Fe-series catalyst of biomass carbon base, comprises the following steps that：
（1）After air-drying pine lignin is size-reduced, ground 100 mesh sieve after 40-50 DEG C of drying of low temperature；
（2）Weigh 2.5 g collagens to be placed in 15 mL water, collagen aqueous solution is formed in heating for dissolving at 65 DEG C, and
7.5 g lignin are added, the wherein mass ratio of collagen and lignin is 1:3, it is slow to said mixture in whipping process
The mL of ferric chloride solution 5 of 7.14 mol/L is added dropwise, it is 20 % that the volume of wherein iron chloride is calculated in mass percent；Blending homogeneous
After be placed under the conditions of 20-25 DEG C of room temperature and be aged 30 min；Vacuum drying obtains to constant weight under being subsequently placed in 60 DEG C of atmosphere of temperature
Obtain biomass carbon base Fe-series catalyst presoma, ground 100 mesh sieve；
（3）Above-mentioned biomass carbon base Fe-series catalyst presoma is positioned in tube type vacuum atmospheric resistance furnace, in nitrogen protection
Under, 400 DEG C are warming up to the rate of heat addition of 5 DEG C/min, naturally cool to room temperature, ground 100 mesh sieve after 4 h of insulation；
（4）By step（3）The sample of middle acquisition is in OH-Concentration be 0.1 mol/L dilute alkaline soln in wash 20 min;Then
Ion-cleaning to neutrality is spent, the biomass carbon base Fe-series catalyst of functionalization can be obtained after heating, drying.
2nd, catalytic wet hydrogen peroxide oxidation high concentration chemical nickel plating waste solution
High concentration chemical nickel plating waste solution is mainly derived from Shenzhen industrial park board production enterprise, and its water quality characteristic is：
COD 45000-50000 mg/L, Ni2+4700 mg/L, Cu2+100 mg/L, pH 5.3.
Specific method for treating waste liquid, it is as follows：
（1）Presetting chemical nickel plating waste solution pH value is added to 100 mL chemical platings 3 g biomass carbon base Fe-series catalysts to after 3
In nickel waste liquid, stirred and evenly mixed under the conditions of the rpm of speed 700；
（2）It is continuous that 3 mL H are added dropwise2O2（30 wt%）Into above-mentioned mixed system, 120 min are reacted under stirring；
（3）Reaction adjusts pH value to 9-11 after terminating by 1 mol/L NaOH solutions, is stirred under the conditions of the rpm of speed 150
15 min, precipitation is separated after centrifugal action, is taken supernatant and is determined nickel ion concentration.
As shown in Figure 7 and Figure 8, the water outlet Ni after above method treatment2+Concentration is down to 1012 mg/L by 1407 mg/L, goes
Except rate up to 28.1 %.
Embodiment 5
First, biomass carbon base Fe-series catalyst is prepared
The preparation method of biomass carbon base Fe-series catalyst, comprises the following steps that：
（1）After air-drying pine lignin is size-reduced, ground 100 mesh sieve after 40-50 DEG C of drying of low temperature；
（2）Weigh 2.5 g collagens to be placed in 15 mL water, collagen aqueous solution is formed in heating for dissolving at 65 DEG C, and
7.5 g lignin are added, the wherein mass ratio of collagen and lignin is 1:3, it is slow to said mixture in whipping process
The mL of ferric chloride solution 5 of 14.29 mol/L is added dropwise, it is 40% that the volume of wherein iron chloride is calculated in mass percent；Blending homogeneous
After be placed under the conditions of 20-25 DEG C of room temperature and be aged 30 min；Vacuum drying obtains to constant weight under being subsequently placed in 60 DEG C of atmosphere of temperature
Obtain biomass carbon base Fe-series catalyst presoma, ground 100 mesh sieve；
（3）Above-mentioned biomass carbon base Fe-series catalyst presoma is positioned in tube type vacuum atmospheric resistance furnace, in nitrogen protection
Under, 800 DEG C are warming up to the rate of heat addition of 1 DEG C/min, naturally cool to room temperature, ground 100 mesh sieve after 1 h of insulation；
（4）By step（3）The sample of middle acquisition is in OH-Concentration be 0.1 mol/L dilute alkaline soln in wash 30 min;Then
Ion-cleaning to neutrality is spent, the biomass carbon base Fe-series catalyst of functionalization can be obtained after heating, drying.
2nd, catalytic wet hydrogen peroxide oxidation high concentration chemical nickel plating waste solution
High concentration chemical nickel plating waste solution is mainly derived from Shenzhen industrial park board production enterprise, and its water quality characteristic is：
COD 45000-50000 mg/L, Ni2+4700 mg/L, Cu2+100 mg/L, pH 5.3.
Specific method for treating waste liquid, it is as follows：
（1）Presetting chemical nickel plating waste solution pH value is added to 100 mL chemical nickel platings 3 g biomass carbon base Fe-series catalysts to 8
In waste liquid, stirred and evenly mixed under the conditions of the rpm of speed 700；
（2）It is continuous that 3 mL H are added dropwise2O2（30 wt%）Into above-mentioned mixed system, 120 min are reacted under stirring；
（3）Reaction adjusts pH value to 9-11 after terminating by 1 mol/L NaOH solutions, is stirred under the conditions of the rpm of speed 150
15 min, precipitation is separated after centrifugal action, is taken supernatant and is determined nickel ion concentration.
As shown in Figure 9 and Figure 10, the water outlet Ni after above method treatment2+Concentration is down to 364 mg/L by 1040 mg/L, goes
Except rate is up to 65.0 %.
Above content is to combine specific preferred embodiment further description made for the present invention, it is impossible to assert
Specific implementation of the invention is confined to these explanations.For general technical staff of the technical field of the invention,
On the premise of not departing from present inventive concept, some simple deduction or replace can also be made, should be all considered as belonging to of the invention
Protection domain.
Claims (10)
1. a kind of preparation method of biomass carbon base Fe-series catalyst, it is characterised in that it is comprised the following steps：
Step S1：Prepare collagen aqueous solution；
Step S2：Lignin is added in the collagen aqueous solution, and adds inorganic molysite solution, be aged after blending homogeneous
20~60 min；Then vacuum drying is ground and obtains grinding product to constant weight；
Step S3：By the grinding product under the conditions of inert gas shielding, it is warming up to the rate of heat addition of 1-10 DEG C/min
400-1000 DEG C, natural cooling after insulation 1-4 h, then be ground, obtain biomass carbon base Fe-series catalyst sample.
2. the preparation method of biomass carbon base Fe-series catalyst according to claim 1, it is characterised in that：The iron system lives
Property volume of the component on carrier be 5-40wt%, the quality of the carrier for quality and the lignin of collagen quality it
With.
3. the preparation method of biomass carbon base Fe-series catalyst according to claim 2, it is characterised in that：In step S2,
The ratio between mass fraction of iron contained in the collagen, lignin and inorganic molysite is 1：3：（0.2~1.6）.
4. the preparation method of the biomass carbon base Fe-series catalyst according to claim 1 ~ 3 any one, it is characterised in that：
Also include step S4：The sample is washed in alkaline solution, is then washed with deionized to neutrality, after heating, drying i.e.
Obtain the biomass carbon base Fe-series catalyst of functionalization.
5. the preparation method of biomass carbon base Fe-series catalyst according to claim 4, it is characterised in that：In step S1,
Collagen is placed in distilled water, stirring and dissolving obtains collagen aqueous solution under the conditions of 60-70 DEG C.
6. the preparation method of biomass carbon base Fe-series catalyst according to claim 5, it is characterised in that：In step S2,
The advanced sector-style of lignin is dry, break process, and vacuum drying is used to constant weight after grinding sieving.
7. the preparation method of biomass carbon base Fe-series catalyst according to claim 6, it is characterised in that：The lignin
The temperature for carrying out vacuum drying is 40-50 DEG C；In step S4, the OH of alkaline solution-Concentration is 0.1 ~ 0.2 mol/L.
8. the preparation method of the biomass carbon base Fe-series catalyst according to claim 1 ~ 3 any one, it is characterised in that：
The lignin is at least one of hardwood quality or soi lwood lignin；The collagen sources are got a foothold in pigskin, ox bone, process hides
Material or aquatic livestock；The inorganic molysite is at least one in iron chloride or ferric nitrate.
9. a kind of application of biomass carbon base Fe-series catalyst, it is characterised in that：The biomass carbon base Fe-series catalyst is used
The preparation method of the biomass carbon base Fe-series catalyst as described in claim 1 ~ 8 any one is prepared, and it is applied and is urging
In change wet-type peroxide oxidizing degraded chemical nickel plating waste solution.
10. the application of biomass carbon base Fe-series catalyst according to claim 9, it is characterised in that it includes following step
Suddenly：
Step A：The pH value of presetting chemical nickel plating waste solution is added to chemical plating the biomass carbon base Fe-series catalyst to 3-8
In nickel waste liquid, stir and evenly mix and obtain mixed system, the input amount of the biomass carbon base Fe-series catalyst is every liter of chemical nickel plating
Waste liquid puts into 10 ~ 50g；
Step B：To adding H in the mixed system2O2Solution, reacts 20-30 min under stirring；Wherein, the H2O2Press
It is 3.33 ~ 16.65g according to every liter of chemical nickel plating waste solution addition；
Step C：Alkaline solution is subsequently adding, to 9-11, precipitation is centrifuged regulation pH value after stirring, takes supernatant and determines nickel
Ion concentration.
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