CN106423062A - Preparation method of orange-peel-based adsorbent for removing hexavalent chromium ions in water - Google Patents

Preparation method of orange-peel-based adsorbent for removing hexavalent chromium ions in water Download PDF

Info

Publication number
CN106423062A
CN106423062A CN201610938863.2A CN201610938863A CN106423062A CN 106423062 A CN106423062 A CN 106423062A CN 201610938863 A CN201610938863 A CN 201610938863A CN 106423062 A CN106423062 A CN 106423062A
Authority
CN
China
Prior art keywords
orange peel
powder
hexavalent chromium
orange
room temperature
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201610938863.2A
Other languages
Chinese (zh)
Inventor
陈树沛
周梓庄
吴侨旭
陈艳卿
高均贤
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Individual
Original Assignee
Individual
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Individual filed Critical Individual
Priority to CN201610938863.2A priority Critical patent/CN106423062A/en
Publication of CN106423062A publication Critical patent/CN106423062A/en
Pending legal-status Critical Current

Links

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
    • 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
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • 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
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/12—Naturally occurring clays or bleaching earth
    • 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
    • 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
    • C02F2101/22—Chromium or chromium compounds, e.g. chromates

Abstract

The invention discloses a preparation method of an orange-peel-based adsorbent for removing hexavalent chromium ions in water. Firstly, orange peel waste is cleaned up, cut into pieces and crushed into orange peel powder, then sodium bentonite is added to the orange peel powder, mixed powder is mixed with a zinc chloride solution, an obtained mixed liquid is impregnated at the room temperature, calcined in a muffle and then cooled naturally to the room temperature, an obtained material is crushed into intermediate powder and soaked in a hydrochloric acid solution, then the intermediate powder is washed to be neutral with tap water, and finally, the orange-peel-based adsorbent is obtained after drying. The orange peels are used as a main base material and subjected to deep carbonization and activation treatment, and a water treatment agent which has an advanced pore structure, a high specific surface area and good adsorption performance for hexavalent chromium ions is prepared, the environmental stress is relieved, the use cost of the adsorbent is reduced, the utilization way of clay mineral bentonite is added, the selection of hexavalent chromium ion adsorbents is enlarged, and the method has broad actual application prospect.

Description

A kind of orange peel base adsorbent preparation method for removing hexavalent chromium in eliminating water
Technical field
The present invention relates to technical field of water pollution treatment, it is related to one kind raw material based on orange peel and prepares Cr VI in water The method of ion adsorbent.
Background technology
With the industrial expansions such as China's intermetallic composite coating, plating electrolysis, leather tanning, dyeing and chromate, an invention huge sum of money Belong to the impact to environmental ecology for the pollutant also increasingly serious.And in numerous pollutant, the pollution of hexavalent chromium is extensive by people Concern, becomes the prominent environmental problem currently urgently properly settled.Chromium is typically stored in water in two forms, i.e. Cr (III) and Cr (Ⅵ).Because of Cr (VI) ease of solubility, oxidisability and the high osmosis to skin, the toxicity of Cr (VI) is 500 times of Cr (III), by people Class is drunk and into internal, liver, kidney, stomach and intestine is caused to damage, and can cause carcinogenic, is classified as by IARC of the World Health Organization First kind carcinogen.
Go hexavalent chromium in eliminating water common method have absorption method, chemical precipitation method, ion-exchange, membrane separation process, Extraction and biological treatment etc..Wherein, absorption method because equipment simple, the low feature of easy to operate, operating cost and extensive Using.The hexavalent chromium adsorbent commonly used at present mostly is activated carbon, but because charcoal absorption has obvious defect：(1) valency Lattice are expensive, and use cost is higher；(2) poor selectivity, range is limited；(3) generating apparatus are few again, and costly, regeneration is difficult.For Find the new sources of adsorbent material, it is strong and non-secondary pollution that many scholars invest wide material sources, reproducibility sight Agricultural wastes, make inexpensive, continuable adsorbent using agro-ecology discarded object, for water and wastewater treatment, including Heavy metal in adsorption treatment waste water, organic pollution, dyestuff etc..
The many areas of south China are a large amount of to plant oranges and tangerines, and mandarine yield is very high, is only second to Brazil and the U.S..Orange peel area Other orange peel can make dried orange peel and be used as medicine, and most of orange peel is often simply discarded, and causes very big waste, and it is dirty to bring environment Dye problem.Orange peel contains abundant chemical composition, and its surface has multiple chemical groups can participate in adsorption reaction, simultaneously its surface There is lamella, fold or loose structure again, so that specific surface area is increased, be conducive in theory being acted on adsorbate.How sharp It is technical problem urgently to be resolved hurrily with the adsorbent that orange peel is prepared into hexavalent chromium in removable water.
Content of the invention
The technical problem to be solved in the present invention is to provide a kind of orange peel base adsorbent for removing hexavalent chromium in eliminating water Preparation method, the adsorbent of its preparation can effectively remove hexavalent chromium in eliminating water, reduces adsorbent use cost, improves economic effect Benefit.
In order to solve above-mentioned technical problem, a kind of orange peel base adsorbent for removing hexavalent chromium in eliminating water of the present invention Preparation method, comprises the following steps：
A. cut into 1cm after orange peel discarded object being cleaned up2Fritter, with 105 DEG C of temperature in electric drying oven with forced convection Degree places drying 2～4 hours, is then ground into the orange peel powder of 40～60 mesh；
B. sodium bentonite is added in described orange peel powder, both mix and obtain mixed-powder, described sodium base is swollen Profit soil is 0.1～0.15 with the mass ratio of orange peel powder:1；
C. prepare the liquor zinci chloridi that mass fraction is 15%～20%, by feed liquid mass ratio 1:2～4 by described mixed powder End is mixed with liquor zinci chloridi, stirs, and obtains mixed liquor and impregnates 12～24 hours at room temperature；
D. mixed liquor is placed in Muffle furnace so as to be heated to 500～600 DEG C from room temperature, roasting at this temperature 90～120 minutes, then naturally cool to room temperature；
E. the material powder obtained by step D is broken into the intermediate powder of 30～60 mesh, this intermediate powder is placed in quality and divides Number soaks in the hydrochloric acid solution for 10% 12～24 hours, and then the pH value with water washing from the beginning to cleaning solution is neutral, finally Dry 2～4 hours at a temperature of 105 DEG C, obtain orange peel base adsorbent.
Described orange peel is the skin of Rutaceae citrus fruit.
The montmorillonite that mass fraction is 80% is included in described sodium bentonite, its granularity/mesh number >=200 mesh, expand Hold for 25～50ml/g, cation exchange capacity (CEC) CEC >=70mmol/100g.
The pH value of described cleaning solution is 7, using the inspection of pH test paper.
The present invention is modified to orange peel, adds sodium bentonite to strengthen intensity and the water stability of finished product, profit simultaneously Improve the adsorption effect of adsorbent with the suction-operated of sodium bentonite.In the dipping process using liquor zinci chloridi, chlorination Zinc ion in zinc solution enters in the middle of the hole of orange peel, makes orange peel fiber that swollen hydrolysis, oxygen occur in charing, activation process Changing the reaction such as degraded, catalytic dehydration, form pore structure, increasing the specific surface area of orange peel, thus increasing absorption property.Hydrochloric acid is clear Wash and finally play a part to dredge duct and activating adsorbent.
The invention has the beneficial effects as follows：, as a kind of agricultural wastes, it is using there being obvious advantage for orange peel：One is yield Greatly, wide material sources；Two is that cost of material is cheap；Three be raw material concentrate；Four is with social benefit, economic benefit and Environmental Effect Benefit, not only can slow down the pollution to environment but also can improve the value of orange peel discarded object.The present invention utilizes resourceful orange peel For main basic material, carry out charing, the activation process of depth, prepare and make that pore structure is flourishing, specific surface area is high, to six Valency chromium ion has the water treatment agent of good adsorption properties, alleviates the pressure of environment, reduces adsorbent use cost, simultaneously Increased the bentonitic utilization ways of clay mineral, the selection of the hexavalent chromium adsorbent of expansion, having wide reality should Use prospect.
Specific embodiment
Embodiment 1：
A kind of orange peel base adsorbent preparation method for removing hexavalent chromium in eliminating water, comprises the following steps：
A. take the orange peel discarded object of 100g, after orange peel discarded object is cleaned up, cut into 1cm2Fritter, electric heating drum Placed with 105 DEG C of temperature in wind drying box and dry 2 hours, be then ground into the orange peel powder of 50 mesh；
B. take 10g orange peel powder, 1g sodium bentonite is added thereto, mixes and obtain mixed-powder；
C. prepare the liquor zinci chloridi that mass fraction is 20%, by feed liquid mass ratio 1:4 by described mixed-powder and chlorination Zinc solution mixes, and stirs, and obtains mixed liquor and impregnates 24 hours at room temperature；
D. mixed liquor is placed in Muffle furnace so as to be heated to 600 DEG C from room temperature, 90 points of roasting at this temperature Clock, then naturally cools to room temperature；
E. the material powder obtained by step D is broken into the intermediate powder of 60 mesh, this intermediate powder is placed in mass fraction is Soak in 10% hydrochloric acid solution 6 hours, then the pH value with water washing from the beginning to cleaning solution is neutral, finally in 105 DEG C of temperature Degree is lower to dry 2 hours, obtains orange peel base adsorbent.
Orange peel base adsorbent 8.6g is added 1L to contain in the water of 50mg/L hexavalent chromium, at room temperature with 180 revs/min Speed stirs 50 minutes, then filters or centrifugation, in water outlet after process, hexavalent chromium can meet《Integrated wastewater discharges Standard》(GB8978-2002) and《Plating pollutant emission standard》(GB21900-2008) requirement.
Embodiment 2：
A kind of orange peel base adsorbent preparation method for removing hexavalent chromium in eliminating water, comprises the following steps：
A. take the orange peel discarded object of 100g, after orange peel discarded object is cleaned up, cut into 1cm2Fritter, electric heating drum Placed with 105 DEG C of temperature in wind drying box and dry 3 hours, be then ground into the orange peel powder of 40 mesh；
B. take 10g orange peel powder, 1.5g sodium bentonite is added thereto, mixes and obtain mixed-powder；
C. prepare the liquor zinci chloridi that mass fraction is 15%, by feed liquid mass ratio 1:3 by described mixed-powder and chlorination Zinc solution mixes, and stirs, and obtains mixed liquor and impregnates 12 hours at room temperature；
D. mixed liquor is placed in Muffle furnace so as to be heated to 550 DEG C from room temperature, 100 points of roasting at this temperature Clock, then naturally cools to room temperature；
E. the material powder obtained by step D is broken into the intermediate powder of 40 mesh, this intermediate powder is placed in mass fraction is Soak in 10% hydrochloric acid solution 6 hours, then the pH value with water washing from the beginning to cleaning solution is neutral, finally in 105 DEG C of temperature Degree is lower to dry 4 hours, obtains orange peel base adsorbent.
Orange peel base adsorbent 6.1g is added 1L to contain in the water of 25mg/L hexavalent chromium, at room temperature with 150 revs/min Speed stirs 40 minutes, then filters or centrifugation, in water outlet after process, hexavalent chromium can meet《Integrated wastewater discharges Standard》(GB8978-2002) and《Plating pollutant emission standard》(GB21900-2008) requirement.
Embodiment 3：
A kind of orange peel base adsorbent preparation method for removing hexavalent chromium in eliminating water, comprises the following steps：
A. take the orange peel discarded object of 100g, after orange peel discarded object is cleaned up, cut into 1cm2Fritter, electric heating drum Placed with 105 DEG C of temperature in wind drying box and dry 2 hours, be then ground into the orange peel powder of 60 mesh；
B. take 10g orange peel powder, 1.2g sodium bentonite is added thereto, mixes and obtain mixed-powder；
C. prepare the liquor zinci chloridi that mass fraction is 18%, by feed liquid mass ratio 1:2 by described mixed-powder and chlorination Zinc solution mixes, and stirs, and obtains mixed liquor and impregnates 20 hours at room temperature；
D. mixed liquor is placed in Muffle furnace so as to be heated to 500 DEG C from room temperature, 100 points of roasting at this temperature Clock, then naturally cools to room temperature；
E. the material powder obtained by step D is broken into the intermediate powder of 30 mesh, this intermediate powder is placed in mass fraction is Soak in 10% hydrochloric acid solution 6 hours, then the pH value with water washing from the beginning to cleaning solution is neutral, finally in 105 DEG C of temperature Degree is lower to dry 3 hours, obtains orange peel base adsorbent.
Orange peel base adsorbent 9.9g is added 1L to contain in the electroplating wastewater of 197mg/L hexavalent chromium, at room temperature with 200 Rev/min speed stir 50 minutes, then filter or centrifugation, in water outlet after process, hexavalent chromium can meet《Sewage Comprehensive discharge standard》(GB8978-2002) and《Plating pollutant emission standard》(GB21900-2008) requirement.
Orange peel base adsorbent prepared by the method for the present invention is used for the removal of hexavalent chromium in the water quality such as waste water, absorption The consumption of agent be 5～10kg/t sewage, under stirring action reaction adsorb the complete time be 30～50 minutes, specifically used can basis Actual conditions adjust usage amount.
The foregoing is only the preferred embodiments of the present invention, as long as realize the skill of the object of the invention with essentially identical means Art scheme broadly falls within protection scope of the present invention.

Claims (4)

1. a kind of orange peel base adsorbent preparation method for removing hexavalent chromium in eliminating water is it is characterised in that include following walking Suddenly：
(A) cut into 1cm after orange peel discarded object being cleaned up2Fritter, put with 105 DEG C of temperature in electric drying oven with forced convection Put drying 2～4 hours, be then ground into the orange peel powder of 40～60 mesh；
(B) sodium bentonite is added in described orange peel powder, both mix and obtain mixed-powder, described sodium bentonite Mass ratio with orange peel powder is 0.1～0.15:1；
(C) prepare the liquor zinci chloridi that mass fraction is 15%～20%, by feed liquid mass ratio 1:2～4 by described mixed-powder Mix with liquor zinci chloridi, stir, obtain mixed liquor and impregnate 12～24 hours at room temperature；
(D) mixed liquor is placed in Muffle furnace so as to be heated to 500～600 DEG C from room temperature, at this temperature roasting 90～ 120 minutes, then naturally cool to room temperature；
(E) material powder obtained by step D is broken into the intermediate powder of 30～60 mesh, this intermediate powder is placed in mass fraction is Soak in 10% hydrochloric acid solution 12～24 hours, then the pH value with water washing from the beginning to cleaning solution is neutral, finally 105 Dry 2～4 hours at a temperature of DEG C, obtain orange peel base adsorbent.
2. the orange peel base adsorbent preparation method for removing hexavalent chromium in eliminating water according to claim 1, its feature It is：Described orange peel is the skin of Rutaceae citrus fruit.
3. the orange peel base adsorbent preparation method for removing hexavalent chromium in eliminating water according to claim 1, its feature It is：The montmorillonite that mass fraction is 80% is included in described sodium bentonite, its granularity/mesh number >=200 mesh, expansion capacity is 25～50ml/g, cation exchange capacity (CEC) CEC >=70mmol/100g.
4. the orange peel base adsorbent preparation method for removing hexavalent chromium in eliminating water according to claim 1, its feature It is：The pH value of described cleaning solution is 7, using the inspection of pH test paper.
CN201610938863.2A 2016-10-31 2016-10-31 Preparation method of orange-peel-based adsorbent for removing hexavalent chromium ions in water Pending CN106423062A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610938863.2A CN106423062A (en) 2016-10-31 2016-10-31 Preparation method of orange-peel-based adsorbent for removing hexavalent chromium ions in water

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610938863.2A CN106423062A (en) 2016-10-31 2016-10-31 Preparation method of orange-peel-based adsorbent for removing hexavalent chromium ions in water

Publications (1)

Publication Number Publication Date
CN106423062A true CN106423062A (en) 2017-02-22

Family

ID=58179152

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610938863.2A Pending CN106423062A (en) 2016-10-31 2016-10-31 Preparation method of orange-peel-based adsorbent for removing hexavalent chromium ions in water

Country Status (1)

Country Link
CN (1) CN106423062A (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106984065A (en) * 2017-03-14 2017-07-28 中国地质大学（武汉） A kind of method of scene separation chromium form
CN110255556A (en) * 2019-06-27 2019-09-20 清华大学 The method that the porous material of pollution of chromium in water removal is removed in the modified Chinese parasol leaf production of the concentrated sulfuric acid
CN110935421A (en) * 2019-12-17 2020-03-31 扬州大学 Method for adsorption treatment of hexavalent chromium-containing wastewater by bismuth ferrite modified charcoal compound
CN112275254A (en) * 2020-10-14 2021-01-29 四川长晏科技有限公司 Wastewater treatment agent and preparation method and application thereof
CN113023953A (en) * 2021-03-25 2021-06-25 浙江建设职业技术学院 Advanced treatment method for sewage of paper mill

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103933936A (en) * 2014-04-08 2014-07-23 昆明理工大学 Preparation method and application of antibiotic composite adsorbent

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103933936A (en) * 2014-04-08 2014-07-23 昆明理工大学 Preparation method and application of antibiotic composite adsorbent

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
中山大学生物系生化微生物教研室编: "《生化技术导论》", 30 September 1978 *
熊道陵等编著: "《废铬资源再利用技术》", 31 October 2012, 北京：冶金工业出版社 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106984065A (en) * 2017-03-14 2017-07-28 中国地质大学（武汉） A kind of method of scene separation chromium form
CN110255556A (en) * 2019-06-27 2019-09-20 清华大学 The method that the porous material of pollution of chromium in water removal is removed in the modified Chinese parasol leaf production of the concentrated sulfuric acid
CN110935421A (en) * 2019-12-17 2020-03-31 扬州大学 Method for adsorption treatment of hexavalent chromium-containing wastewater by bismuth ferrite modified charcoal compound
CN112275254A (en) * 2020-10-14 2021-01-29 四川长晏科技有限公司 Wastewater treatment agent and preparation method and application thereof
CN113023953A (en) * 2021-03-25 2021-06-25 浙江建设职业技术学院 Advanced treatment method for sewage of paper mill

Similar Documents

Publication Publication Date Title
CN106423062A (en) Preparation method of orange-peel-based adsorbent for removing hexavalent chromium ions in water
CN107162093A (en) A kind of aquaculture water purifying agent and preparation method thereof
CN105170091A (en) Preparation method of iron-modified reed biological carbon, and application of iron-modified reed biological carbon in treatment of phosphorus wastewater
CN106512950A (en) Preparation method of surfactant-modified zeolite adsorbent
CN108467036B (en) Desiliconized rice hull-based activated carbon and preparation method and application thereof
CN103464111B (en) Softex kw modification walnut shell adsorbent and its preparation method and application
CN106967442A (en) A kind of Cadmium in Soil passivator and preparation method and application
CN104787764A (en) Method for preparing active carbon from radix astragali waste residues
CN105854807A (en) Composite adsorbing material based on straw and preparation method thereof
CN103303917B (en) Activated carbon and preparation process thereof
CN104743556B (en) Powder active carbon prepared by using turf as raw material and preparation method of powder active carbon
CN101913675A (en) Method for removing phosphorus in water by modifying waste egg shell
CN105080499A (en) Methylene blue dye adsorbent and preparation and application method thereof
CN104495843A (en) Method for making activated carbon by using wild peach pit shells
CN108101055A (en) Grape slag sludge base high-performance bio carbon and preparation method and application
CN104193061B (en) A kind of processing method of paraquat agricultural chemicals waste water
CN106512937A (en) Preparation method of adsorbent for efficiently removing methylene blue in wastewater
CN102220135B (en) Leaching liquid for repairing organic phenol-contaminated soil and reparation method of organic phenol-contaminated soil
CN112251236B (en) Preparation and application method of plant-derived soil multi-metal eluting agent
CN107880894A (en) A kind of preparation method and application of Cd-Pb contaminated soil repair materials
CN104176736A (en) Method for preparing activated carbon from ionic liquid pretreated raw material
CN104307490A (en) Preparation method of alginate-persimmon tannin composite material
CN106693884A (en) Heavy metal adsorbent and preparing method and application thereof
CN106334535A (en) Preparation method of adsorbing material for removing Congo red in dye wastewater
CN105692845A (en) Preparing technology for shaddock peel natural coagulants

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
WD01 Invention patent application deemed withdrawn after publication
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20170222