CN109626486A - A kind of method of coupling processing high concentrated organic wastewater and heavy metal wastewater thereby - Google Patents
A kind of method of coupling processing high concentrated organic wastewater and heavy metal wastewater thereby Download PDFInfo
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- CN109626486A CN109626486A CN201811642745.2A CN201811642745A CN109626486A CN 109626486 A CN109626486 A CN 109626486A CN 201811642745 A CN201811642745 A CN 201811642745A CN 109626486 A CN109626486 A CN 109626486A
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- heavy metal
- wastewater
- high concentrated
- concentrated organic
- organic wastewater
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- 239000002351 wastewater Substances 0.000 title claims abstract description 113
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 90
- 238000000034 method Methods 0.000 title claims abstract description 35
- 238000012545 processing Methods 0.000 title claims abstract description 31
- 230000008878 coupling Effects 0.000 title claims abstract description 26
- 238000010168 coupling process Methods 0.000 title claims abstract description 26
- 238000005859 coupling reaction Methods 0.000 title claims abstract description 26
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 45
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000005416 organic matter Substances 0.000 claims abstract description 33
- 239000003610 charcoal Substances 0.000 claims abstract description 32
- 238000010521 absorption reaction Methods 0.000 claims abstract description 31
- 239000003054 catalyst Substances 0.000 claims abstract description 30
- 238000003795 desorption Methods 0.000 claims abstract description 14
- 239000007789 gas Substances 0.000 claims abstract description 14
- 230000008569 process Effects 0.000 claims abstract description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000001257 hydrogen Substances 0.000 claims abstract description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 11
- 239000002699 waste material Substances 0.000 claims abstract description 11
- 230000001590 oxidative effect Effects 0.000 claims abstract description 7
- 238000003837 high-temperature calcination Methods 0.000 claims abstract description 6
- 239000011148 porous material Substances 0.000 claims abstract description 5
- 150000002500 ions Chemical class 0.000 claims description 26
- 238000000926 separation method Methods 0.000 claims description 16
- 238000001354 calcination Methods 0.000 claims description 15
- 239000002994 raw material Substances 0.000 claims description 14
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000002028 Biomass Substances 0.000 claims description 8
- 230000004913 activation Effects 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 229910052793 cadmium Inorganic materials 0.000 claims description 7
- 239000002006 petroleum coke Substances 0.000 claims description 7
- 238000003763 carbonization Methods 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 239000012190 activator Substances 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 229920001971 elastomer Polymers 0.000 claims description 5
- 229910052737 gold Inorganic materials 0.000 claims description 5
- 239000001307 helium Substances 0.000 claims description 5
- 229910052734 helium Inorganic materials 0.000 claims description 5
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000004033 plastic Substances 0.000 claims description 5
- 229920003023 plastic Polymers 0.000 claims description 5
- 238000004064 recycling Methods 0.000 claims description 5
- 239000005060 rubber Substances 0.000 claims description 5
- 238000012216 screening Methods 0.000 claims description 5
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- 229910021645 metal ion Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M potassium chloride Inorganic materials [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 3
- 238000006057 reforming reaction Methods 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims 1
- 238000001833 catalytic reforming Methods 0.000 abstract description 5
- 230000008929 regeneration Effects 0.000 abstract description 4
- 238000011069 regeneration method Methods 0.000 abstract description 4
- 230000002779 inactivation Effects 0.000 abstract description 3
- 238000002474 experimental method Methods 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 9
- 239000003463 adsorbent Substances 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 4
- 238000002407 reforming Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 241000251468 Actinopterygii Species 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 2
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 2
- 235000011613 Pinus brutia Nutrition 0.000 description 2
- 241000018646 Pinus brutia Species 0.000 description 2
- 208000005374 Poisoning Diseases 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- 238000005255 carburizing Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000003651 drinking water Substances 0.000 description 2
- 235000020188 drinking water Nutrition 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910001453 nickel ion Inorganic materials 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- 239000002352 surface water Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 241000282412 Homo Species 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 231100000570 acute poisoning Toxicity 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000010814 metallic waste Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000000243 photosynthetic effect Effects 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000007420 reactivation Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 210000000697 sensory organ Anatomy 0.000 description 1
- 235000015170 shellfish Nutrition 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/34—Regenerating or reactivating
- B01J20/3416—Regenerating or reactivating of sorbents or filter aids comprising free carbon, e.g. activated 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/34—Regenerating or reactivating
- B01J20/3483—Regenerating or reactivating by thermal treatment not covered by groups B01J20/3441 - B01J20/3475, e.g. by heating or cooling
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/005—Separation by a physical processing technique only, e.g. by mechanical breaking
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
Abstract
A kind of method of coupling processing high concentrated organic wastewater and heavy metal wastewater thereby, carbonaceous material is prepared to the porous carbon material with high-specific surface area and abundant pore structure after carbonization-activation, for coupling processing high concentrated organic wastewater and heavy metal wastewater thereby and prepares hydrogen-rich gas.Porous carbon material prepared by waste materials containing carbon is respectively used to the absorption enrichment of organic matter and heavy metal ion in high concentrated organic wastewater and heavy metal wastewater thereby, realizes the removing of heavy metal and organic matter.The porous carbon material for having adsorbed heavy metal ion is prepared into support type carbon base catalyst through high-temperature calcination, the organic matter desorbed in the porous charcoal of organic matter has been adsorbed for catalytic reforming and has prepared hydrogen-rich gas.For cycle applications in the absorption of high concentrated organic wastewater, the carbon base catalyst of inactivation recycles heavy metal by oxidizing roasting after the porous charcoal desorption completely of absorption enrichment organic matter.Water source used in catalytic reforming experiment is the water that absorption is isolated after the completion, achievees the purpose that the treatment of wastes with processes of wastes against one another and resource regeneration with this.
Description
Technical field
The invention belongs to field of waste water treatment, and in particular to a kind of coupling processing high concentrated organic wastewater and heavy metal wastewater thereby
Method.
Background technique
Currently, the water resource pollution problem in China is got worse, become urgent need to resolve in the national economic development one is big
Problem.With the development of society, industrialized production is continuously increased, industrial wastewater discharge is also increasingly severe, and many enterprises will be big
The industrial wastewater of amount is directly discharged into river or bay, not only influences aquatic ecosystem, also seriously threatens human health.Various cokes
Change waste water, pharmacy waste water, textile printing and dyeing wastewater, petrochemical wastewater and belongs to high concentrated organic wastewater, it is difficult during processing
It spends very big.
Organic concentration is high in high concentrated organic wastewater, and general COD is in 2000mg/L or more；BOD value is lower, biochemical place
The difficulty of reason is larger, complicated component；The coloration of high concentrated organic wastewater is high, peculiar smell is big；There is strong acid and strong base, if directly arranged
It puts, can not only cause the discomfort on people's sense organ, meeting block sunlight irradiates the water surface later into water body, causes microorganism and water in water
Plant photosynthetic rate reduces, and causes aquatic ecological to change, causes the death of water fish class He other aquatic animals.High concentration
The many kinds of substance such as sulfide, nitride in organic wastewater are permeated the ground by surface water, can be straight after being quoted by humans and animals
It connects and jeopardizes human health, even result in death.Also, high concentrated organic wastewater contains Gao Fang in the water outlet Jing Guo common process
Fragrance Organic Compounds, will affect surface water quality, increase cost to subsequent drinking water treatment.
Heavy metal wastewater thereby be discharged in the industrial processes such as mining and metallurgy, machine-building containing heavy metal (typically contain nickel,
The heavy metals such as copper, mercury, chromium, cadmium, arsenic, lead, zinc) waste water, heavy metal have enriching, be difficult to degrade in the environment.With a huge sum of money
Belonging to the heavy metal that discharge of wastewater goes out can also accumulate even if concentration very little in algae and bed mud, be adsorbed by fish and shellfish body surface,
Food chain concentration is generated, to cause public hazards.And heavy metal can occur strongly in human body with protein and various enzymes
Interaction inactivates them, it is also possible to it is enriched in certain organs in human body, it, will more than the limit that human body is resistant to
Human body acute poisoning, subacute poisoning or slow poisoning are caused, very big harm is caused to human body.For example, the Minamata that Japan occurs
Sick (mercury pollution) and itai-itai (cadmium pollution) etc. are all as caused by heavy metal pollution.At present for high concentrated organic wastewater and again
The processing of metallic wastewater can use active carbon adsorption, but the regeneration of active carbon and elution are relatively difficult.Have in view of high concentration
The complexity and refractory organics of machine waste water and heavy metal wastewater thereby ingredient, and use adsorbent limitation, study a kind of coupling
The method for closing processing high concentrated organic wastewater and heavy metal wastewater thereby, it is significant to ecological environmental protection and safe drinking water.
Summary of the invention
It is an object of the invention to be directed to above-mentioned the problems of the prior art, a kind of coupling processing high concentration organic waste is provided
The method of water and heavy metal wastewater thereby, prepared using carbonaceous materials such as biomass, waste plastics, scrap rubbers with high-specific surface area and
The porous carbon material of abundant pore structure, be respectively used in high concentrated organic wastewater and heavy metal wastewater thereby organic matter and heavy metal from
The absorption enrichment of son, prepares support type carbon base catalyst through high-temperature calcination for the porous carbon material for having adsorbed heavy metal ion, uses
Hydrogen-rich gas is prepared in the organic matter desorbed in porous charcoal of the catalytic reforming by having adsorbed useless Organic substance in water, is realized with useless system
Useless and resource regeneration.
To achieve the goals above, the method for coupling processing high concentrated organic wastewater and heavy metal wastewater thereby of the present invention include with
Lower step:
Step 1: carbon raw material is carried out carbonization treatment after pretreatment, gained carbonized stock is mixed it with activator
Afterwards, under an inert atmosphere, the porous carbon material with high-specific surface area and abundant pore structure is prepared by heating activation；
Step 2: porous charcoal and water are consolidated using the organic matter in porous carbon material absorption high concentrated organic wastewater
Liquid separation obtains the porous charcoal and the first separation water of absorption enrichment organic matter；Using in porous carbon material absorption heavy metal wastewater thereby
Heavy metal ion, porous charcoal and water are separated by solid-liquid separation, obtain absorption enriching heavy metal ion porous charcoal and second point
From water；
Step 3: the porous charcoal of absorption enrichment organic matter is placed in progress thermal desorption processing in desorption chamber, it is enriched with absorption
Organic matter in porous carbon material surface and duct is desorbed in the form of gaseous volatile in thermal histories, obtains gas
State volatile matter, the porous charcoal after desorption are recycling in the organic matter in absorption high concentrated organic wastewater；By an absorption enrichment huge sum of money
The porous charcoal for belonging to ion forms support type carbon base catalyst after high-temperature calcination under an inert atmosphere, for adsorbing heavy metal ion
Porous carbon material be equivalent to catalyst carrier, and the heavy metal ion being adsorbed in porous carbon surface and duct is equivalent to activity
Component；
Step 4: gaseous volatile is imported to the reformer chamber for being placed with support type carbon base catalyst, gaseous volatile hair
Raw reforming reaction, reaction water source are derived from the first separation water and the second separation water, are converted into hydrogen-rich gas；
Step 5: realizing the recycling of heavy metal after oxidizing roasting to the carbon base catalyst inactivated after reaction.
It includes shell, stalk, wood that the carbon raw material, which selects petroleum coke, biomass, scrap rubber or waste plastics, biomass,
Bits.
Pretreatment described in step 1 includes broken, screening and is dried.
Activator in step 1 is KOH, ZnCl2、H3PO4、NaOH、FeCl3, KCl and K2CO3At least one of.
Inert atmosphere described in step 1 is provided by nitrogen, argon gas or helium, and the range of activation temperature is 400~900
℃。
COD is in 2000~30000mg/L, BOD/COD < 0.3 in the water of high concentrated organic wastewater.
The content of beary metal of the heavy metal wastewater thereby is 0.1~100g/L.
Heating temperature of the step three in thermal desorption treatment process is 100~300 DEG C.
The step five carries out oxidizing roasting under air atmosphere or oxygen atmosphere, and calcination temperature is 600~900 DEG C.
Inert atmosphere described in step 3 is provided by nitrogen, argon gas or helium, and calcination temperature is 500~1000 DEG C；
Heavy metal wastewater thereby refers to the heavy metal wastewater thereby containing at least one of metal ion Ni, Cu, Fe, Co, Cd and Au.
Heavy metal ion of the supported charcoal base Catalyst Adsorption in porous carbon surface and duct include metal from
One of sub- Ni, Cu, Fe, Co, Cd and Au or a variety of.
Compared with prior art, the present invention is with following the utility model has the advantages that the raw material sources for preparing porous carbon material are wide
It is general, including the carbonaceous materials such as petroleum coke, biomass (such as shell, stalk, sawdust), damaged tire, scrap rubber, waste plastics, it is made
Adsorbent material have high-specific surface area and high stability, adsorption effect is good, and preparation process is simple, is obtaining efficient adsorbent
While can also reduce pollution of the waste to environment.Porous carbon material provided by the invention is in absorption enriching heavy metal waste water
Heavy metal ion after, can by reduction calcining obtaining support type carbon base catalyst, for adsorbing the porous carbon of heavy metal
Material is equivalent to catalyst carrier, and the heavy metal ion being adsorbed in porous carbon surface and duct is equivalent to active component, one
Determine the problem of the problem of heavy metal recovery is handled after conventional carbon desorbs and adsorbent reactivation are alleviated in degree, while
Realize solidification and the efficient resource of heavy metal in waste water.High concentrated organic wastewater and heavy metal wastewater thereby coupling provided by the invention
Close processing method, be not related to bioreactor, when operation relatively flexibly, it is simple process, at low cost, and secondary dirt will not be generated
Dye.The present invention is by the porous carbon material prepared using carbonaceous material to high concentrated organic wastewater and containing the waste water of heavy metal ion
Adsorbed, can effectively realize the removing of heavy metal ions in wastewater and organic matter, greatly reduce subsequent water process at
This and time, and adsorb the later porous carbon material of heavy metal and can be prepared into the catalysis of supported charcoal base by high-temperature calcination
Agent, the catalyst can prepare hydrogen-rich gas by the organic matter desorbed in catalytic reforming porous charcoal, not only realize high concentration
The coupling processing of organic wastewater and heavy metal wastewater thereby, also achievees the purpose that the treatment of wastes with processes of wastes against one another and resource regeneration.
Detailed description of the invention
The process flow chart of Fig. 1 coupling processing high concentrated organic wastewater and heavy metal wastewater thereby of the present invention；
In attached drawing: 1- carbon raw material；2- porous carbon material；3- high concentrated organic wastewater；The porous charcoal of 4- enrichment organic matter；
5- first separates water；6- gaseous volatile；Porous charcoal after 7- desorption；The carbon base catalyst of 8- inactivation；9- supported charcoal base is urged
Agent；10- second separates water；The porous charcoal of 11- enriching heavy metal ion；12- heavy metal wastewater thereby.
Specific embodiment
The present invention is described in further detail with reference to the accompanying drawings and embodiments.
Referring to Fig. 1, the method for coupling processing high concentrated organic wastewater and heavy metal wastewater thereby of the present invention the following steps are included:
Step 1: by the carbon raw materials such as petroleum coke, biomass, scrap rubber, waste plastics 1 through the pre- place such as broken, screening, dry
Carbonization treatment is carried out after reason, after gained carbonized stock and chemical activating agent are mixed, under an inert atmosphere, by heating activation system
The standby porous carbon material 2 for providing high-specific surface area and abundant pore structure；Activator is KOH, ZnCl2、H3PO4、NaOH、
FeCl3, KCl and K2CO3At least one of, the range of activation temperature is 400~900 DEG C.
Step 2: after being used to the porous carbon material 2 of step 1 preparation to adsorb the organic matter in high concentrated organic wastewater 3,
Porous charcoal and water are subjected to solid- liquid separation, the porous charcoal 4 and first for obtaining absorption enrichment organic matter decomposes water 5；By step 1 system
After standby porous carbon material 2 is used to adsorb the heavy metal ion in heavy metal wastewater thereby 12, porous charcoal and water are subjected to solid-liquid point
From the porous charcoal 11 and second for obtaining absorption enriching heavy metal ion decompose water 10；COD is equal in the water of high concentrated organic wastewater 3
In 2000~30000mg/L, BOD/COD < 0.3.The content of beary metal of heavy metal wastewater thereby 12 is 0.1~100g/L.
Step 3: the porous charcoal 4 of the absorption enrichment organic matter obtained after solid- liquid separation in step 2 is placed in desorption chamber
Middle progress thermal desorption processing, makes the organic matter being enriched in porous carbon material surface and duct volatilize in thermal histories with gaseous state
The form of object 6 desorbs.Heating temperature in desorption process is generally 100~300 DEG C, and the porous charcoal 7 after the completion of desorbing can
With organic matter of the cycle applications in absorption high concentrated organic wastewater 3；By the absorption obtained after solid- liquid separation in step 2 richness
The porous charcoal 11 for collecting heavy metal ion forms support type carbon base catalyst 9 after high-temperature calcination under an inert atmosphere, for adsorbing
The porous carbon material of heavy metal ion is equivalent to catalyst carrier, and the heavy metal ion being adsorbed in porous carbon surface and duct
It is equivalent to active component.The carbon base catalyst of formation can be containing one of metal ions such as Ni, Cu, Fe, Co, Cd, Au or
It is a variety of.Calcination temperature employed in catalyst preparation process is generally 500~1000 DEG C.
For the oxidation for preventing porous charcoal in calcination process, calcination process uses the inert gases such as nitrogen, argon gas, helium to protect
Protect gas.Meanwhile it is solidificated in the heavy metal ion being adsorbed in porous charcoal on porous carbon material by calcining；
Step 4: the gaseous volatile 6 that desorption evaporates is imported to the weight for being pre-placed support type carbon base catalyst 9
Whole interior, gaseous volatile 6 with reforming reaction occurs in the contact process of support type carbon base catalyst 9, be converted into hydrogen rich gas
Body.Reaction water source is a part in the first separation water 5 and the second separation water 10, and another part is through subsequent processing direct emission；
Step 5: after catalytic reforming reaction, for the carbon base catalyst 8 of inactivation, a huge sum of money is realized after oxidizing roasting
The recycling of category.The temperature of oxidizing roasting is generally 600~900 DEG C, carries out under air atmosphere or oxygen atmosphere.
Technical effect of the invention is illustrated by the following examples:
Embodiment 1
The method of coupling processing high concentrated organic wastewater and heavy metal wastewater thereby of the present invention the following steps are included:
Step 1: the preparation of carbon raw material 1: using pine sawdust as raw material, by pine sawdust after broken, screening, dry
It is carbonized, carbon raw material 1 is prepared, 700 DEG C of carburizing temperature, the carbonization treatment time is 2h.
Step 2: the preparation of porous carbon material 2: by biomass-based carbonized stock and potassium hydroxide made from step 1 with 1:4
Ratio mixing after, reacted in fixed bed reactors, it is multiple with pickling and washing after reaction, be dried to obtain porous charcoal
Material 2, the activation temperature of carbon raw material 1 in the process are 700 DEG C, reaction time 2h.
Step 3: coupling processing high concentrated organic wastewater and heavy metal wastewater thereby: the porous carbon material 2 that step 2 is produced is divided
Not Yong Yu in high concentrated organic wastewater 3 and heavy metal wastewater thereby 12 organic matter and heavy metal absorption.Taking COD content is 7000mg/L
The porous carbon material 2 of 0.8g step 2 preparation, after the completion of absorption, waste water are added into waste water water by high concentrated organic wastewater 100ml
The removal rate of middle organic matter is 95%.The heavy metal wastewater thereby for being 10g/L containing nickel ion concentration is taken, 0.8g step is added into waste water water
The porous carbon material 2 of rapid two preparation, after the completion of absorption, the removal rate of heavy metal in waste water is 95%.
Step 4: preparing support type carbon base catalyst 9: the porous carbon material 2 of Ni ion will be adsorbed with by reduction calcining
Support type carbon base catalyst 9 is prepared, calcination temperature is 600 DEG C, calcination time 6h.
Step 5: catalytically reforming hydrogen producing is studied: the support type carbon base catalyst 9 in step 4 is used for catalytic reformer step
Adsorb the organic matter desorbed on the porous carbon material 2 of organic matter in three, 600 DEG C of reforming temperature, gained hydrogen yield 73%.
Embodiment 2
The method of coupling processing high concentrated organic wastewater and heavy metal wastewater thereby of the present invention the following steps are included:
Step 1: the preparation of carbon raw material 1: using petroleum coke as raw material, petroleum coke being carried out after broken, screening, drying
Carbon raw material 1 is prepared in carbonization, and 700 DEG C of carburizing temperature, the carbonization treatment time is 2h.
Step 2: the preparation of porous carbon material 2: by petroleum coke carbonized stock and potassium hydroxide made from step 1 with 1:4's
After ratio mixing, reacted in fixed bed reactors, it is multiple with pickling and washing after reaction, it is dried to obtain porous carbon
Material, the activation temperature of carbonized stock in the process are 700 DEG C, are 2h between hair is seasonable.
Step 3: coupling processing high concentrated organic wastewater and heavy metal wastewater thereby: the porous carbon material 2 that step 2 is produced is divided
Not Yong Yu in high concentrated organic wastewater 3 and heavy metal wastewater thereby 12 organic matter and heavy metal absorption.Taking COD content is 7000mg/L
The porous carbon material 2 of 0.8g step 2 preparation, after the completion of absorption, waste water are added into waste water water by high concentrated organic wastewater 100ml
The removal rate of middle organic matter is 98%.The heavy metal wastewater thereby for being 10g/L containing nickel ion concentration is taken, 0.8g step is added into waste water water
The porous carbon material 2 of rapid two preparation, after the completion of absorption, the removal rate of heavy metal in waste water is 98%.
Step 4: preparing support type carbon base catalyst 9: being adsorbed with the porous carbon material 2 of Ni ion by reduction calcining
Support type carbon base catalyst 9 is prepared, calcination temperature is 700 DEG C, calcination time 3h.
Step 5: catalytically reforming hydrogen producing is studied: the support type carbon base catalyst 9 in step 4 is used for catalytic reformer step
Adsorb the organic matter desorbed on the porous carbon material 2 of organic matter in three, 600 DEG C of reforming temperature, gained hydrogen yield 78%.
The above is only presently preferred embodiments of the present invention, not to do restriction in any form to the present invention,
It will be apparent to a skilled person that technical solution of the present invention is also under conditions of not departing from spirit of that invention principle
Several modifications or simple replacement can be carried out, these modifications and replacement also can fall into the protection limited by submitted claim
Within the scope of.
Claims (10)
1. a kind of method of coupling processing high concentrated organic wastewater and heavy metal wastewater thereby, which comprises the following steps:
Step 1: carbon raw material (1) is carried out carbonization treatment after pretreatment, gained carbonized stock is mixed it with activator
Afterwards, under an inert atmosphere, the porous carbon material with high-specific surface area and abundant pore structure is prepared by heating activation
(2)；
Step 2: separation of solid and liquid is adsorbed using the organic matter in porous carbon material (2) absorption high concentrated organic wastewater (3)
It is enriched with the porous charcoal (4) and the first separation water (5) of organic matter；Using in porous carbon material (2) absorption heavy metal wastewater thereby (12)
Heavy metal ion is separated by solid-liquid separation the porous charcoal (11) for obtaining absorption enriching heavy metal ion and the second separation water (10)；
Step 3: the porous charcoal (4) of absorption enrichment organic matter is placed in progress thermal desorption processing in desorption chamber, it is enriched in absorption
Organic matter in porous carbon material surface and duct desorbs in thermal histories in the form of gaseous volatile (6), desorption
Porous charcoal (7) afterwards is recycling in the organic matter in absorption high concentrated organic wastewater (3)；Enriching heavy metal ion will be adsorbed
Porous charcoal (11) forms support type carbon base catalyst (9) after high-temperature calcination under an inert atmosphere, for adsorbing heavy metal ion
Porous carbon material (2) be catalyst carrier, being adsorbed on heavy metal ion in porous carbon surface and duct is active component；
Step 4: gaseous volatile (6) to be imported to the reformer chamber for being placed with support type carbon base catalyst (9), gaseous volatile
(6) reforming reaction occurs, reaction water source is derived from the first separation water (5) and the second separation water (10), is converted into hydrogen-rich gas；
Step 5: realizing the recycling of heavy metal after oxidizing roasting to the carbon base catalyst (8) inactivated after reaction.
2. the method for coupling processing high concentrated organic wastewater and heavy metal wastewater thereby according to claim 1, it is characterised in that: institute
It includes shell, stalk, sawdust that the carbon raw material (1) stated, which selects petroleum coke, biomass, scrap rubber or waste plastics, biomass,.
3. the method for coupling processing high concentrated organic wastewater and heavy metal wastewater thereby according to claim 1, it is characterised in that: step
Pretreatment described in rapid one includes broken, screening and is dried.
4. the method for coupling processing high concentrated organic wastewater and heavy metal wastewater thereby according to claim 1, it is characterised in that: step
Activator described in rapid one is KOH, ZnCl2、H3PO4、NaOH、FeCl3, KCl and K2CO3At least one of.
5. the method for coupling processing high concentrated organic wastewater and heavy metal wastewater thereby according to claim 1, it is characterised in that: step
Inert atmosphere described in rapid one is provided by nitrogen, argon gas or helium, and the range of activation temperature is 400~900 DEG C.
6. the method for coupling processing high concentrated organic wastewater and heavy metal wastewater thereby according to claim 1, it is characterised in that: institute
COD is in 2000~30000mg/L, BOD/COD < 0.3 in the water for the high concentrated organic wastewater (3) stated.
7. the method for coupling processing high concentrated organic wastewater and heavy metal wastewater thereby according to claim 1, it is characterised in that: institute
The content of beary metal for the heavy metal wastewater thereby (12) stated is 0.1~100g/L.
8. the method for coupling processing high concentrated organic wastewater and heavy metal wastewater thereby according to claim 1, it is characterised in that: institute
Heating temperature of the step of the stating three in thermal desorption treatment process is 100~300 DEG C.
9. the method for coupling processing high concentrated organic wastewater and heavy metal wastewater thereby according to claim 1, it is characterised in that: institute
The step of stating five carries out oxidizing roasting under air atmosphere or oxygen atmosphere, and calcination temperature is 600~900 DEG C.
10. the method for coupling processing high concentrated organic wastewater and heavy metal wastewater thereby according to claim 1, it is characterised in that:
Inert atmosphere described in step 3 is provided by nitrogen, argon gas or helium, and calcination temperature is 500~1000 DEG C；
The heavy metal wastewater thereby (12) refers to the heavy metal containing at least one of metal ion Ni, Cu, Fe, Co, Cd and Au
Waste water, the heavy metal ion that the support type carbon base catalyst (9) is adsorbed in porous carbon surface and duct include metal from
One of sub- Ni, Cu, Fe, Co, Cd and Au or a variety of.
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