CN108585439A - A method of detaching metallic particles from cupric zinc organic sludge - Google Patents

A method of detaching metallic particles from cupric zinc organic sludge Download PDF

Info

Publication number
CN108585439A
CN108585439A CN201810202593.8A CN201810202593A CN108585439A CN 108585439 A CN108585439 A CN 108585439A CN 201810202593 A CN201810202593 A CN 201810202593A CN 108585439 A CN108585439 A CN 108585439A
Authority
CN
China
Prior art keywords
reactor
temperature
metallic particles
heavy
fluid
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.)
Granted
Application number
CN201810202593.8A
Other languages
Chinese (zh)
Other versions
CN108585439B (en
Inventor
张同环
陈鑫
赵熙
刘齐鲁
董立忠
周仕学
韩宗盈
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.)
Shandong University of Science and Technology
Original Assignee
Shandong University of Science and Technology
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 Shandong University of Science and Technology filed Critical Shandong University of Science and Technology
Priority to CN201810202593.8A priority Critical patent/CN108585439B/en
Publication of CN108585439A publication Critical patent/CN108585439A/en
Application granted granted Critical
Publication of CN108585439B publication Critical patent/CN108585439B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F11/00Treatment of sludge; Devices therefor
    • C02F11/18Treatment of sludge; Devices therefor by thermal conditioning
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B03SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03BSEPARATING SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS
    • B03B5/00Washing granular, powdered or lumpy materials; Wet separating
    • B03B5/28Washing granular, powdered or lumpy materials; Wet separating by sink-float separation
    • B03B5/30Washing granular, powdered or lumpy materials; Wet separating by sink-float separation using heavy liquids or suspensions
    • B03B5/36Devices therefor, other than using centrifugal force
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F11/00Treatment of sludge; Devices therefor
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F11/00Treatment of sludge; Devices therefor
    • C02F11/004Sludge detoxification
    • 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
    • C10B1/00Retorts
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/10Inorganic compounds
    • C02F2101/20Heavy metals or heavy metal compounds

Abstract

The present invention discloses a kind of method that metallic particles is detached in the zinc organic sludge from cupric, carries out according to the following steps:(1) cupric zinc organic sludge is placed in reactor, with the gas in argon gas metathesis reactor;(2) reactor is heated to 100 DEG C, keeps the temperature 15 20min, temperature is then risen to 160~200 DEG C, keep the temperature 10 15min;(3) after the completion of distilling, reactor is continued into heating and carries out dry distillation charring, controls 400~550 DEG C of pyrolysis temperature, heating rate 10~20 DEG C/min, 40~70min of constant temperature time;It is cooled to room temperature after the completion of destructive distillation in the case where completely cutting off air conditions;(4) it crushes:Destructive distillation solid product after cooling is crushed, is milled, powder is obtained;(5) it sorts:Powder is put into heavy-fluid, is stirred, is then allowed to stand, hypostasis is filtered recycling with filtration method.The present invention can detach metallic particles with sticky organic matter under the conditions of ensureing metallic particles being basically unchanged property of physico-chemical property, and simple for process, cost is relatively low, and metal recovery rate is high.

Description

A method of detaching metallic particles from cupric zinc organic sludge
Technical field
The present invention relates to a kind of organic sludge as resources methods, concretely relate to one kind from cupric zinc organic sludge The method for detaching metallic particles.
Background technology
During brass-plated steel wire wet type drawing, steel wire is inevitably worn when across mold, under abrasion This part coating come, which can enter with lubricating fluid in silt basin, to precipitate.Therefore, in addition to containing based on aliphatic acid in sludge Lubricating fluid organic component outside, also contain a large amount of brass wire particles, as shown in Figure 1.Sludge copper content after natural sedimentation 20% or more, contain 11% or more zinc, far above current copper mine mining grade (<2%) and the mining grade of zinc ore (<1%), Therefore the value of great recycling metal.However the brass wire grain graininess in sludge is evenly dispersed in viscous in micro/nano level In thick lubricating fluid sludge, the adhesion strength of organic matter is stronger, and the two is also difficult to disperse in aqueous solution, therefore is consolidated with traditional Liquid separating method is difficult to detach the two.Answer the requirement of environmental protection, cupric zinc organic sludge that cannot arbitrarily stack simultaneously, at present mostly Number drawn steel wire manufacturing enterprise does not have the technology of oneself processing sludge, often other unit's environmental protection company is entrusted to be handled, from And higher transportation cost and high processing cost are needed, and it is direct burning-that environmental protection company, which handles the general method of producer, Waste residue again extract the mode of metal and carry out Treatment of Copper zinc organic sludge respectively by melting.Sludge is after high temperature incineration, Huang therein Copper particle has been converted to CuO or Zn3(PO4)2, then melting carries copper or to carry zinc all relatively difficult, and cost is higher.
Invention content
Based on above-mentioned technical problem, the present invention proposes a kind of method that metallic particles is detached in the zinc organic sludge from cupric, This method can detach metallic particles with sticky organic matter under the conditions of ensureing metallic particles being basically unchanged property of physico-chemical property.
The adopted technical solution is that:
A method of it detaching metallic particles from cupric zinc organic sludge, carries out according to the following steps:
(1) air-discharging:Cupric zinc organic sludge is placed in reactor, with the gas in argon gas metathesis reactor;
(2) it distills:Reactor is heated to 100 DEG C, keeps the temperature 15-20min, temperature is then risen to 160~200 DEG C, is protected Warm 10-15min;
(3) dry distillation charring:After the completion of distillation, by reactor continue heating carry out dry distillation charring, control pyrolysis temperature 400~ 550 DEG C, heating rate 10~20 DEG C/min, 40~70min of constant temperature time;It is cooled to after the completion of destructive distillation in the case where completely cutting off air conditions Room temperature obtains destructive distillation solid product after cooling;
(4) it crushes:Destructive distillation solid product after cooling is crushed, is milled, powder is obtained;
(5) it sorts:The heavy-fluid that density is 1.3~1.5Kg/L is prepared with zinc chloride, the powder of step (4) is put into heavy-fluid In, stirring makes powder granule fully disperse in heavy-fluid, then stops stirring, heavy-fluid is stood 5~8min, density is more than The brass particle of heavy-fluid density, which will sink, becomes hypostasis, and the charing particle that density is less than heavy-fluid density then floats as float, uses Hypostasis is filtered recycling by filtration method.
Preferably, in dry distillation charring step, while destructive distillation gas-phase product is recycled, is used for combustion heat supplying or power generation.
Preferably, in pulverising step, control mog is that 325 mesh screenings quality are more than 80%.
Preferably, in sorting step, control mixing time is 3~5min.
The method have the benefit that:
The present invention is using the technique of distillation-dry distillation charring-crushing-sorting to organic sticky dirt containing copper zinc metallic particles Mud is handled, can be under the conditions of ensureing metallic particles being basically unchanged property of physico-chemical property, by metallic particles and sticky organic matter point From operability is strong, simple for process, and cost is relatively low, and metal recovery rate is high.
The principle on which of the present invention approximately as:
Organic thick sludge containing metallic particles is steamed first in an inert atmosphere, under organic matter boiling temperature It evaporates, recycles organic matter therein as much as possible and it is dry to carry out heating again to distillation system after rear sludge quality to be distilled no longer reduces It evaporates, makes the organic component for failing to distill out that complicated chemical reaction occur, including pyrolytic reaction, polycondensation reaction etc. finally make dirt Organic matter carbonizing molding in mud.It is just no longer sticky after organic matter carbonizing, it is easy and metal under certain mechanicals efforts Sludge after molding is carried out grinding according to the disseminated grain size size of metal in sludge particle, metal is enable to reach single by grain separation Body dissociates, and is finally separated metallic particles with the method for heavy-liquid concentration.Gravity treatment principle:Organic matter in sludge is through destructive distillation carbon After chemical conversion type, density is about 1.2g/cm3, the density of ormolu particle is about 8.6g/cm3, the two density variation is apparent, very It is easy to be isolated with the heavy-fluid of certain density.
Description of the drawings
Fig. 1 shows the microscope photograph of cupric zinc organic sludge;
Fig. 2 shows the microscope photographs after sludge dry distillation charring.
Specific implementation mode
The present invention proposes that a kind of method that metallic particles is detached in the zinc organic sludge from cupric, this method can ensure metal Under the conditions of being basically unchanged property of particle physico-chemical property, metallic particles is detached with sticky organic matter.
To Mr. Yu's steel wire drawing enterprise production the organic sludge of particle containing brass for, recycle wherein brass particle the step of And condition is as follows:
(1) air-discharging:Brass particle organic sludge will be contained to be placed in reactor, in inert gas argon gas metathesis reactor Gas, metallic particles therein is aoxidized after being heated the purpose is to reduce sludge of logical inert gas.
(2) it distills:Reactor is heated to 100 DEG C, and keeps the temperature the regular hour, fraction at this temperature is mainly that water steams Then temperature is risen to 160~200 DEG C by vapour, soaking time depending on water content in sludge is how many, which is profit used The boiling point warm area of lubricating oil, for distillation time depending on content of organics in sludge, principle is that sludge distills Mass lost in 5min Rate is less than 1%.
(3) dry distillation charring:After the completion of distillation, heats up to reactor and carry out dry distillation charring, and recycle destructive distillation gas-phase product, it can For combustion heat supplying or power generation.400~550 DEG C of pyrolysis temperature, heating rate 10~20 DEG C/min, 40~70min of constant temperature time. Pyrolysis temperature is too low or heating rate is too fast, and low molecular weight hydrocarbons release is incomplete;Pyrolysis temperature is excessively high or heating rate mistake Slowly, sludge compression strength increases after charing, is unfavorable for crushing, while can also increase energy consumption.In isolation air item after the completion of destructive distillation It is cooled to room temperature under part.
(4) it crushes:It can be analyzed according to the microscope photograph 2 after sludge dry distillation charring, metal in sludge grain graininess is equal 40 μm of <, therefore the sludge needs after charing are milled to -325 mesh (- 44 μm), that is, are less than 325 the polished standard screens, can just basically reach Monomer dissociation.Destructive distillation solid product after cooling be crushed-be milled, mog is that -325 mesh are more than 80%, i.e. 325 mesh The amount of screenings matter is more than 80%.
(5) it sorts:The method sorting brass particle of heavy-liquid concentration can be used in mixed powder after metallic monomer dissociation.Use chlorine Change zinc and prepare the heavy-fluid that density is 1.3~1.5, the powder of step (4) is put into heavy-fluid, 3min is stirred, powder granule is made to exist Fully disperse in heavy-fluid, then stop stirring, heavy-fluid is stood into 5~8min, the brass particle that density is more than heavy-fluid density will Sinking becomes hypostasis, and the charing particle that density is less than heavy-fluid then floats as float, is then filtered hypostasis with filtration method Recycling.It is detected through XRD, the hypostasis particle of recycling is still ormolu, and redox reaction does not occur substantially.
The present invention is further explained in the light of specific embodiments:
Embodiment 1
20g sludge sample 1 (aqueous 15.6%, brass 34.1%) is taken, is put into distillation reactor, reactor is discharged with argon gas In air, reactor is then warming up to 100 DEG C, and constant temperature 20min, the moisture in sludge is discharged.By distillation reactor temperature Degree rises to 160 DEG C, and constant temperature 10min collects out fraction 3.7ml.Then reactor is warming up to 400 DEG C with the rate of 10 DEG C/min Destructive distillation, constant temperature 45min, then cooled to room temperature under protection of argon gas are carried out, solid product quality is 9.4g after carbonization.It will do It evaporates solid product to be put into planetary ball mill, with the rotating speed ball milling 2min of 180r/min, powder, which is then placed in density, is In the zinc chloride heavy-fluid of 1.3Kg/L, 3min is stirred, 5min is then allowed to stand, float is outwelled, filter out the hypostasis in heavy-fluid, and Drying is weighed, and hypostasis 6.9g is obtained, and copper zinc mass fraction is 95.3% in hypostasis after testing, and thus can calculate the brass rate of recovery is 96.4%.
Embodiment 2
20g sludge sample 2 (aqueous 12.5%, brass 37.7%) is taken, is put into distillation reactor, reactor is discharged with argon gas In air, reactor is then warming up to 100 DEG C, and constant temperature 15min, the moisture in sludge is discharged.By distillation reactor temperature Degree rises to 170 DEG C, and constant temperature 15min collects out fraction 4.1ml.Then reactor is warming up to 450 DEG C with the rate of 12 DEG C/min Destructive distillation, constant temperature 70min, then cooled to room temperature under protection of argon gas are carried out, solid product quality is 10.3g after carbonization.It will Destructive distillation solid product is put into planetary ball mill, and with the rotating speed ball milling 2.5min of 180r/min, powder is then placed in density In the zinc chloride heavy-fluid of 1.4Kg/L, to stir 3min, being then allowed to stand 6min, float is outwelled, filter out the hypostasis in heavy-fluid, And drying is weighed, and hypostasis 7.7g is obtained.Copper zinc mass fraction is 96.1% in hypostasis after testing, thus can calculate the brass rate of recovery It is 98.1%.
Embodiment 3
20g sludge sample 2 (aqueous 12.5%, brass 37.7%) is taken, is put into distillation reactor, reactor is discharged with argon gas In air, reactor is then warming up to 100 DEG C, and constant temperature 15min, the moisture in sludge is discharged.By distillation reactor temperature Degree rises to 180 DEG C, and constant temperature 15min collects out fraction 4.5ml.Then reactor is warming up to 500 DEG C with the rate of 15 DEG C/min Destructive distillation, constant temperature 60min, then cooled to room temperature under protection of argon gas are carried out, solid product quality is 9.2g after carbonization.It will do It evaporates solid product to be put into planetary ball mill, with the rotating speed ball milling 2min of 240r/min, powder, which is then placed in density, is In the zinc chloride heavy-fluid of 1.5Kg/L, 3min is stirred, 8min is then allowed to stand, float is outwelled, filter out the hypostasis in heavy-fluid, and Drying is weighed, and hypostasis 7.5g is obtained.Copper zinc mass fraction is 97.8% in hypostasis after testing, and thus can calculate the brass rate of recovery is 97.3%.
Embodiment 4
20g sludge sample 2 (aqueous 12.5%, brass 37.7%) is taken, is put into distillation reactor, reactor is discharged with argon gas In air, reactor is then warming up to 100 DEG C, and constant temperature 15min, the moisture in sludge is discharged.By distillation reactor temperature Degree rises to 200 DEG C, and constant temperature 15min collects out fraction 4.6ml.Then reactor is warming up to 550 DEG C with the rate of 12 DEG C/min Destructive distillation, constant temperature 45min, then cooled to room temperature under protection of argon gas are carried out, solid product quality is 8.7g after carbonization.It will do It evaporates solid product to be put into planetary ball mill, with the rotating speed ball milling 2min of 180r/min, then it is 1.5 that powder, which is placed in density, In zinc chloride heavy-fluid, 3min is stirred, 8min is then allowed to stand, float is outwelled, then filters out the hypostasis in heavy-fluid, and dry title Weight, obtains hypostasis 7.5g.Copper zinc mass fraction is 98.6% in hypostasis after testing, and thus can calculate the brass rate of recovery is 98.1%.

Claims (4)

1. a kind of method for detaching metallic particles in zinc organic sludge from cupric, it is characterised in that carry out according to the following steps:
(1) air-discharging:Cupric zinc organic sludge is placed in reactor, with the gas in argon gas metathesis reactor;
(2) it distills:Reactor is heated to 100 DEG C, keeps the temperature 15-20min, temperature is then risen to 160~200 DEG C, keeps the temperature 10- 15min;
(3) dry distillation charring:After the completion of distillation, reactor is continued into heating and carries out dry distillation charring, controls pyrolysis temperature 400~550 DEG C, heating rate 10~20 DEG C/min, 40~70min of constant temperature time;After the completion of destructive distillation room is cooled in the case where completely cutting off air conditions Temperature obtains destructive distillation solid product after cooling;
(4) it crushes:Destructive distillation solid product after cooling is crushed, is milled, powder is obtained;
(5) it sorts:The heavy-fluid that density is 1.3~1.5Kg/L is prepared with zinc chloride, the powder of step (4) is put into heavy-fluid, is stirred It mixes, powder granule is made fully to disperse in heavy-fluid, then stop stirring, heavy-fluid is stood into 5~8min, it is close that density is more than heavy-fluid The brass particle of degree, which will sink, becomes hypostasis, and the charing particle that density is less than heavy-fluid density then floats as float, uses filtration method Hypostasis is filtered recycling.
2. the method for detaching metallic particles in a kind of zinc organic sludge from cupric according to claim 1, it is characterised in that: In dry distillation charring step, while destructive distillation gas-phase product is recycled, is used for combustion heat supplying or power generation.
3. the method for detaching metallic particles in a kind of zinc organic sludge from cupric according to claim 1, it is characterised in that: In pulverising step, control mog is that 325 mesh screenings quality are more than 80%.
4. the method for detaching metallic particles in a kind of zinc organic sludge from cupric according to claim 1, it is characterised in that: In sorting step, control mixing time is 3~5min.
CN201810202593.8A 2018-03-13 2018-03-13 A method of separating metallic particles from cupric zinc organic sludge Expired - Fee Related CN108585439B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810202593.8A CN108585439B (en) 2018-03-13 2018-03-13 A method of separating metallic particles from cupric zinc organic sludge

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810202593.8A CN108585439B (en) 2018-03-13 2018-03-13 A method of separating metallic particles from cupric zinc organic sludge

Publications (2)

Publication Number Publication Date
CN108585439A true CN108585439A (en) 2018-09-28
CN108585439B CN108585439B (en) 2019-07-19

Family

ID=63626161

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810202593.8A Expired - Fee Related CN108585439B (en) 2018-03-13 2018-03-13 A method of separating metallic particles from cupric zinc organic sludge

Country Status (1)

Country Link
CN (1) CN108585439B (en)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001239298A (en) * 2000-03-02 2001-09-04 Hisao Otake Sludge treating method, and method and apparatus for treating organic waste water using the method
JP2004008957A (en) * 2002-06-07 2004-01-15 Ebara Corp Phosphorus and nitrogen recovery method and apparatus therefor
CN104773935A (en) * 2015-04-27 2015-07-15 岩固(上海)环保科技有限公司 Treatment process for dry distillation carbonization of sludge
CN106564916A (en) * 2016-11-14 2017-04-19 荆门市格林美新材料有限公司 Preparation method for preparing high-quality chromium slag filler and recovering sodium carbonate by using chromium slag

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001239298A (en) * 2000-03-02 2001-09-04 Hisao Otake Sludge treating method, and method and apparatus for treating organic waste water using the method
JP2004008957A (en) * 2002-06-07 2004-01-15 Ebara Corp Phosphorus and nitrogen recovery method and apparatus therefor
CN104773935A (en) * 2015-04-27 2015-07-15 岩固(上海)环保科技有限公司 Treatment process for dry distillation carbonization of sludge
CN106564916A (en) * 2016-11-14 2017-04-19 荆门市格林美新材料有限公司 Preparation method for preparing high-quality chromium slag filler and recovering sodium carbonate by using chromium slag

Also Published As

Publication number Publication date
CN108585439B (en) 2019-07-19

Similar Documents

Publication Publication Date Title
AU663227B2 (en) Process for remediation of lead-contaminated soil and waste battery casings
CN100500600C (en) Integrative recovering and reusing method for heavy metals in wire board plating wastewater treatment sludge
JP2012500110A (en) Disposal of electrical and electronic equipment
KR101815917B1 (en) Equipment and method for producing refined oil using used polymers and titanium refining
US20090193934A1 (en) Process for de-oiling steelmaking sludges and wastewater streams
CN107379322A (en) A kind of tire carbon black circulation utilization method
CN1649981A (en) Method and installation for low-temperature pyrolysis of rubber products, steel/rubber composites, and use of the pyrolysis products
CN108585439B (en) A method of separating metallic particles from cupric zinc organic sludge
US3084029A (en) Recovery of phosphorus from sludge
TWI483918B (en) Cement manufacturing method
CN102229863A (en) Method for recovering grease from oil-containing argil residue by squeezing
WO2014106650A2 (en) Methods and apparatuses for the thermal depolymeriaztion of hydrocarbon-containing starting material
RU2571061C1 (en) Method of producing energy from organic material-containing wastes
CN109628142A (en) A kind of method that high efficiency, low cost removes solid particle in FCC slurry
CN102294345A (en) Method for processing discarded PCBs (printed circuit boards) into composite municipal products
KR101550136B1 (en) Recovery Method Of Aluminium Compound And PMMA From Waste Artificial Marble By Physical And Chemical Treatment
KR101414355B1 (en) Recovering apparatus of Methyl MethAcrylate and Alumina from Waste Artificial Marvel and method using the same
CN205684472U (en) A kind of recycling device scrapping wiring board
JP2000285756A (en) Dechlorination method of coating waste of vinyl chloride coated wire
KR101426137B1 (en) Recovering apparatus of methyl methacrylate and Alumina from waste artificial marvel
CN214991358U (en) Resource utilization and high-efficiency separation system for Fischer-Tropsch wax residues
Ol’shanskaya et al. Recycling of Heavy Metals and Their Compounds from Galvanic Sludges to Produce Pigments and Fillers and the Active Species of Nickel–Iron (Cadmium) Battery Cathodes
Martelo et al. A critical updated review of all stages of the tantalum recycling chain from waste of tantalum capacitors
JP3551958B2 (en) Waste plastic decomposition treatment method and apparatus and fuel
JP4139194B2 (en) Coke production method

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20190719