CN105618025B - A kind of method that low-temperature catalyzed organic waste of sulfonation charcoal prepares biomass carbon - Google Patents

A kind of method that low-temperature catalyzed organic waste of sulfonation charcoal prepares biomass carbon Download PDF

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CN105618025B
CN105618025B CN201610025333.9A CN201610025333A CN105618025B CN 105618025 B CN105618025 B CN 105618025B CN 201610025333 A CN201610025333 A CN 201610025333A CN 105618025 B CN105618025 B CN 105618025B
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sulfonation
biomass carbon
organic waste
carbon
temperature
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CN105618025A (en
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马伟芳
张伟锋
董志刚
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Beijing Dorsun International Technology Development Co ltd
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/18Carbon
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10BDESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B53/00Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10BDESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B53/00Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
    • C10B53/02Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of cellulose-containing material
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10BDESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B57/00Other carbonising or coking processes; Features of destructive distillation processes in general
    • C10B57/14Features of low-temperature carbonising processes
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00Technologies for the production of fuel of non-fossil origin
    • Y02E50/10Biofuels, e.g. bio-diesel

Abstract

The present invention relates to the method that a kind of low-temperature catalyzed organic waste of sulfonation charcoal prepares biomass carbon.Agricultural wastes prepare biomass carbon under medium temperature limited oxygen condition, then biomass carbon is made sulfonation Pd/carbon catalyst after rinsing, freeze-drying, sulfonation efficiency is 1.9~2.5mmol/g with 95%~98% oleum sulfonation.Low-temperature catalyzed organic waste prepares biomass carbon, it is uniformly to mix the organic waste after sulfonation Pd/carbon catalyst, crushing and water by a certain percentage, 1~2h is heated in the closed reactor that temperature is 100~130 DEG C, rotating speed is 60~100 turns/h, reacts and biomass carbon is made.The present invention not only solves the problem of organic waste treatment, and realize inexpensive charcoal processing, its cost only has the 10%~15% of common high temperature charcoal processing, the biomass carbon specific surface area of preparation is big, absorption property is good, the adsorption cleaning of sewage disposal is can be widely applied to, there are good economic and social benefits.

Description

A kind of method that low-temperature catalyzed organic waste of sulfonation charcoal prepares biomass carbon
Technical field
The invention belongs to organic waste to prepare biomass carbon technical field, and more particularly to a kind of sulfonation charcoal is low-temperature catalyzed to be had The method that machine discarded object prepares biomass carbon, includes the preparation method of sulfonation Pd/carbon catalyst.
Background technology
At present, the processing of organic waste is mainly the modes such as landfill, compost, burning, and not only processing cost is high, but also does not have There is the recycling value for giving full play to organic waste, and secondary pollution may be produced in processing procedure.Such as family's animal manure Just usual compost or anaerobic methane production gas utilizes;Agricultural wastes and garden waste are due to taking up a large area, the ratio being incinerated It is very high always, but air can be polluted in burning process, therefore current Land use systems have gasification, biomass block and height are made Temperature biological carbon soil conditioner;And the organic waste such as pharmacy waste residue of the dewatered sludge of municipal sewage plant's biochemistry pool, Chinese medicine The characteristics of processing cost of gurry is very high, and sludge is due to its high-moisture percentage, is always the problem of environmental protection industry (epi), waste residue of Chinese herbs by It is special in its component, it is disposed currently as danger wastes.
In recent years, how the main exploratory development of people effectively handles organic waste, reduces the harm to environment, at reduction Manage cost etc..The patent application of application number CN 201010148039.X and CN 201010161390.2 discloses one kind with farming Thing stalk, resin etc. prepare soil improvement biological carbon and the method for high-energy biological carbon, but these methods are required to more than 400 DEG C Temperature can realize carbonization, and need to carry out under conditions of nitrogen anaerobic is passed through, therefore carbon cost processed is higher, carbon processed is set Standby more complicated, tail gas needs collection to handle.Application number 201010510277.0 discloses a kind of device for manufacturing biological carbon, bag Preheating chamber, destructive distillation room, combustion chamber, the disengaging gentle body retracting device of feed roller are included, not only equipment is complicated, preparation temperature 600~850 DEG C, high energy consumption, and tail gas also needs to special collection and treatment device, therefore seriously affected reclaiming organic waste utilization Process.
At present, studies have reported that biomass catalyzing prepares biodiesel, because catalyst can effectively reduce preparation temperature Degree and pressure.But also sulphur is not prepared using biomass carbon on the low-temperature catalyzed research for preparing biomass carbon of sulfonation carbon Change C catalyst, and the low cost of organic waste low-temperature carbonization, industrialization manufacture biomass carbon are realized using the catalyst Technology and equipment is not reported so far.
The content of the invention
In view of the shortcomings of the prior art, the present invention provides a kind of low-temperature catalyzed organic waste of sulfonation charcoal to prepare biomass carbon Method, include the preparation method of sulfonation Pd/carbon catalyst.
A kind of preparation method of sulfonation Pd/carbon catalyst, it is to utilize medium temperature bar of the agricultural wastes straw at 450~550 DEG C Prepare biomass carbon under part, by after the biomass carbon sulfonation of preparation up to sulfonation Pd/carbon catalyst;Comprise the following steps:
Agricultural wastes are ground into the segment of 1~3cm first, 2~4h is heated under 450~550 DEG C of limited oxygen conditions, from Biomass carbon is prepared into after being so cooled to room temperature, is then totally submerged biomass carbon with 95%~98% oleum, in 100~120 DEG C of 12~16h of sulfonation under limited oxygen condition, it is 4~5 that the sulfonation charcoal after sulfonation, which is filtered, is rinsed to pH, -15 ~-20 DEG C of 16~24h of freeze-drying, up to sulfonation Pd/carbon catalyst.
The agricultural wastes include maize straw, broomcorn straw, wheat stalk, corn ear, peanut shell, rice husk, bacteria stick In one kind and more than.
The aromatic rings ratio of the biomass carbon is more than 2.0mmol/g;The sulfonation efficiency of the sulfonation for 1.9~ 2.5mmol/g。
A kind of method that low-temperature catalyzed organic waste of above-mentioned sulfonation charcoal prepares biomass carbon, comprises the following steps:
(1) preprocessing process:Organic waste after air-drying is crushed to the segment of below 0.5cm, sulfonation charcoal is catalyzed Organic waste aggregate after agent and crushing is (0.5~1) in mass ratio:(98~100) be uniformly mixed, to mixture on uniformly Sprinkling accounts for the water purification of mixture gross weight 0.5%~1%, stirs evenly;
(2) low temperature catalytic processes:The mixture of pretreatment is added in rotary heating reactor, is 100~130 in temperature DEG C closed rotary heating reactor in heat 1~2h, reactor rotating speed is 60~100 turns/h, up to biomass carbon.
The organic waste includes animal waste, agricultural wastes, garden waste, municipal sewage plant's biochemistry pool Dewatered sludge, the pharmacy waste residue of Chinese medicine, one kind in kitchen garbage and more than.
The carbonization degree of the biomass carbon is more than 99%, specific surface area 100m2/ more than g.
Mixture after catalysis biomass carbon processed, crosses the sieve of 0.5cm, online thing is sulfonation Pd/carbon catalyst, can be direct Recycling.
Beneficial effects of the present invention are:
The present invention is using agricultural wastes straw as the matrix for preparing sulfonation charcoal, it is rich in cellulose, prepared by medium temperature Biomass carbon is rich in aromatic ring structure, and specific surface area is big, can readily introduce sulfonic group, realizes the sulfonation efficiency of higher;Sulphur It is good to change reactivity height, the stability of Pd/carbon catalyst, repeats and utilizes.
The low-temperature catalyzed organic waste of sulfonation charcoal of the present invention prepares biomass carbon, and wherein organic waste derives from a wealth of sources, can To be agriculture and forestry organic waste material, the biochemical sludge of sewage treatment plant, pharmacy waste residue etc.;Low-temperature catalyzed carbonization process is simple, the temperature of preparation Degree and time reduce, and have saved energy consumption, have reduced cost, its cost only has the 10%~15% of common high temperature charcoal, And secondary exhaust emission is not produced, organic waste generates the toxic and harmful gas such as bioxin during avoiding high temperature charcoal processing, The processing handling problems of poisonous and harmful organic waste are not only solved, and realize the high added value resource of organic waste Change and utilize, improve the recycle value of organic waste.
The biomass carbon charing ratio of the present invention is high, and specific surface area is big, and adsorption capacity is strong, therefore can be widely applied to sewage The adsorption cleaning technique of processing links, has good economic and social benefit.
Brief description of the drawings
Fig. 1 is scanning electron microscope (SEM) image of sulfonation charcoal prepared by embodiment 1;
Fig. 2 is the scanning electron microscope of agricultural wastes maize straw biomass carbon prepared by embodiment 1;
Fig. 3 is the front and rear infrared spectrum spectrogram with maize straw biomass carbon of sulfonation charcoal sulfonation prepared by embodiment 1;Its In 1 be sulfonation Pd/carbon catalyst raw material;2 be sulfonation Pd/carbon catalyst;3 biomass carbons prepared for maize straw;
Fig. 4 is the scanning electron microscope of Chinese medicine dreg biomass carbon prepared by embodiment 2.
Embodiment
The present invention will be further described with reference to the accompanying drawings and detailed description.It is emphasized that the description below It is merely exemplary, the scope being not intended to be limiting of the invention and its application.
Embodiment 1
Maize straw is broken to the segment of 1~3cm, 2h, cooled to room temperature are heated in the Muffle furnace that 480 DEG C limit oxygen After be prepared into aromatic rings biomass carbon, then biomass carbon is put into the reaction kettle of polytetrafluoro liner, with 98% oleum Acid is totally submerged, the sulfonation 12h under 105 DEG C of limited oxygen conditions, and it is 4.5 that the sulfonation charcoal after sulfonation, which is filtered, is rinsed to pH, -18 Sulfonation Pd/carbon catalyst is made in DEG C freeze-drying 18h.From the SEM image and attached drawing 2 of attached drawing 1, the specific surface area of sulfonation charcoal Greatly, porosity is high, sulphonation rate is high, is respectively 112.5m2/ g, 0.028cm3/ g, 2.4mmol/g.
Agricultural wastes corn stalk powder is broken to below 0.5cm, by the maize straw after sulfonation Pd/carbon catalyst and crushing With mass ratio 1:100 are uniformly mixed, to mixture on uniformly sprinkling account for the water purification of mixture gross weight 1%, stir evenly laggard Enter rotary heating reactor, heat 1h in the closed rotative heater that furnace temperature is 110 DEG C, reactor rotating speed is 60 turns/h, i.e., Biomass carbon is made.From the SEM image of attached drawing 2, the specific surface area of biomass carbon is big, porosity is high, charing ratio is high, point Wei not 121.8m2/ g, 0.031cm3/ g, 99.9%.Polybrominated diphenyl ethers BDE- of the biomass carbon to concentration in sewage for 25 μ g/L 47 maximum adsorption capacity is 15.7mg/g.
Label 1 is the raw material of sulfonation Pd/carbon catalyst in Fig. 3;2 be sulfonation Pd/carbon catalyst;3 lifes prepared for maize straw Material charcoal.Infrared spectrum analysis result shows that the spectral peak of wavelength 1173 or so represents that sulfonation Pd/carbon catalyst has successfully loaded sulfonic acid Base;The infrared spectrum analysis result of biomass carbon shows that biomass carbon association OH vibrations strengthen, in 3439cm-1Place occurs one Stronger peak, it is related with C=C skeletal vibrations;In 1668 and 1659cm-1There is small peak in place, itself and C-H stretching vibrations and C=O Flexible correlation, shows that substituent is gradually decreased or even disappeared in organic matter, sample condensation aggravation, and the performance of armaticity feature is obvious.
Embodiment 2
Herbal pharmaceutical waste residue is crushed to below 0.2cm, after obtained sulfonation Pd/carbon catalyst in embodiment 1 and crushing Waste residue of Chinese herbs is with mass ratio 1:98 are uniformly mixed, to mixture on uniformly sprinkling account for the water purification of mixture gross weight 0.5%, stirring Enter rotary heating reactor after uniformly, heat 2h in the closed rotative heater that furnace temperature is 130 DEG C, reactor rotating speed is 100 turns/h, that is, biomass carbon is made.From the SEM image of attached drawing 4, the specific surface area of biomass carbon is big, porosity is high, charcoal It is high to change ratio, is respectively 100.1m2/ g, 0.019cm3/ g, 99.5%.The biomass carbon is the more of 25 μ g/L to concentration in sewage The maximum adsorption capacity of bromo biphenyl ether BDE-47 is 13.5mg/g.

Claims (4)

1. a kind of method that low-temperature catalyzed organic waste of sulfonation charcoal prepares biomass carbon, it is characterised in that comprise the following steps:
(1) preprocessing process:Organic waste after air-drying is crushed to the segment of below 0.5cm, by sulfonation Pd/carbon catalyst and Organic waste aggregate after crushing is (0.5~1) in mass ratio:(98~100) be uniformly mixed, to mixture on uniformly spray The water purification of mixture gross weight 0.5%~1% is accounted for, is stirred evenly;
(2) low temperature catalytic processes:The mixture of pretreatment is added in rotary heating reactor, is 100~130 DEG C in temperature 1~2h is heated in closed rotary heating reactor, reactor rotating speed is 60~100 turns/h, up to biomass carbon;
The preparation method of sulfonation Pd/carbon catalyst comprises the following steps in step (1):Agricultural wastes are ground into 1~3cm first Segment, 2~4h is heated under 450~550 DEG C of limited oxygen conditions, is prepared into biomass carbon after cooled to room temperature, then will Biomass carbon is totally submerged with 95%~98% oleum, 12~16h of sulfonation under 100~120 DEG C of limited oxygen conditions, by sulphur It is 4~5 that sulfonation charcoal after change, which is filtered, rinsed to pH, 16~24h is freeze-dried at -15~-20 DEG C, up to sulfonation Pd/carbon catalyst;
The agricultural wastes are included in maize straw, broomcorn straw, wheat stalk, corn ear, peanut shell, rice husk, bacteria stick It is a kind of and more than;
The aromatic rings ratio of the biomass carbon is more than 2.0mmol/g;The sulfonation efficiency of the sulfonation is 1.9~2.5mmol/g.
2. according to the method described in claim 1, it is characterized in that, the organic waste includes animal waste, agriculture waste One kind in thing, garden waste, the dewatered sludge of municipal sewage plant's biochemistry pool, the pharmacy waste residue of Chinese medicine, kitchen garbage More than and.
3. according to the method described in claim 1, it is characterized in that, the carbonization degree of the biomass carbon be more than 99%, compare table Area is 100m2/ more than g.
4. the according to the method described in claim 1, it is characterized in that, sieve of the mixture, excessively 0.5cm after catalysis biomass carbon processed Net, online thing are sulfonation Pd/carbon catalyst, can directly be reused.
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CN105855275B (en) * 2016-06-22 2018-12-25 中国科学院城市环境研究所 A kind of processing method of sludge and kitchen garbage
CN112980476A (en) * 2021-01-30 2021-06-18 仲恺农业工程学院 Method for directionally producing aromatic hydrocarbon-rich bio-oil and hydrogen-rich biomass gas
CN114644333A (en) * 2022-03-17 2022-06-21 湖南恒信新型建材有限公司 Preparation method of sulfonated carbon for thermal cracking aromatization of biomass at constant temperature and temperature
CN115975058A (en) * 2022-11-14 2023-04-18 福建星海通信科技有限公司 Cellulose material hydrolysis method

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