CN111777133A

CN111777133A - Preparation method of novel non-hardening coupling iron-carbon micro-electrolysis filler

Info

Publication number: CN111777133A
Application number: CN202010634219.2A
Authority: CN
Inventors: 王廷文; 王晨瑜
Original assignee: Shandong Northern Sanwei Environmental Protection Technology Co ltd
Current assignee: Shandong Northern Sanwei Environmental Protection Technology Co ltd
Priority date: 2020-07-02
Filing date: 2020-07-02
Publication date: 2020-10-16

Abstract

The invention discloses a preparation method of a novel hardening-free coupling iron-carbon micro-electrolysis filler, which comprises the following steps: step 1: taking iron ore powder or iron scale, and crushing and screening to obtain iron powder; step 2: iron powder is filled into the center of a refractory container, reducing agent is filled around the refractory container, the refractory container is sealed and filled into a reducing furnace, and roasting reduction is carried out; and step 3: preparing comprehensive metal powder; and 4, step 4: mixing the paste mixed solution; and 5: synthesizing the pasty mixed liquid of the metal powder mixed slurry, filling the mixed liquid into a refractory container, and filling the refractory container into a high-temperature sintering furnace; step 6: preparing a coupling agent; and 7: adding coupling agent into the comprehensive metal powder, feeding the mixture into a stirrer, fully stirring, mixing, pressing and forming, stacking and aging, spraying water, feeding the mixture into a microwave high-temperature furnace, drying and sintering, cooling to below 30 ℃, discharging, and screening to obtain the novel non-hardening coupling iron-carbon micro-electrolysis filler with the offwhite appearance. Compared with the prior art, the invention has the advantages that: the hardening and passivation of the iron-carbon micro-electrolysis filler is permanently and thoroughly solved.

Description

Preparation method of novel non-hardening coupling iron-carbon micro-electrolysis filler

Technical Field

The invention relates to the field of sewage treatment materials for ecological environment treatment, in particular to a preparation method of a novel non-hardening coupling iron-carbon micro-electrolysis filler.

Background

Chinese water resources occupy a small amount of people and are unbalanced in spatial distribution. With the acceleration of the urbanization and the industrialization of China, the gap of the water resource demand is increasing, the water resource pollution is more and more serious, and a novel material (short for micro-electrolysis material) is urgently needed to treat the water resource pollution problem.

At present, enterprises in chemical industry, electroplating, printing and dyeing, pharmacy, pesticide, landfill leachate, dye, chemical fiber, leather making, slaughtering, coking and the like discharge a great deal of sewage with high concentration, high toxicity, high chroma, high heavy metal and difficult biochemical treatment in the production process, and the sewage is treated by using a traditional scrap iron micro-electrolysis method, an iron powder micro-electrolysis method, a high-temperature clay reduction roasting iron carbon micro-electrolysis filling method, a pressed iron carbon filling method and the like as a pre-pretreatment combined biochemical method at home and abroad. A certain effect is achieved within the operation range of a short time (3-6 months). However, in the traditional iron scrap micro-electrolysis method, the iron powder micro-electrolysis method, the high-temperature reduction roasting iron-carbon micro-electrolysis filler method, the clay pressing iron-carbon filler and the like, hardening and passivation of a large amount of iron-carbon micro-electrolysis fillers occur in long-term operation, the filler is blocked and loses efficacy, the sewage treatment rate is greatly reduced and even completely loses efficacy after the filler is passivated, and a micro-electrolysis sewage water inlet system is blocked and an aeration system is blocked after the filler is hardened, so that the sewage treatment system cannot normally operate. Meanwhile, the traditional microelectrolysis material and the traditional high-temperature reduction roasting iron-carbon microelectrolysis filler cannot solve the problems of hardening and passivation caused by too tight contact between iron and iron in a formula, and also cannot solve the problem that the surface of the iron-carbon microelectrolysis filler is easy to generate a passivation film in the acid sewage operation, so that the long-term operation treatment effect of the microelectrolysis process is increasingly poor, and finally the microelectrolysis process is completely ineffective. The use of the hardened and passivated filler which is taken out of production by a unit increases the sludge amount and solid waste, thus causing resource waste and cost increase.

Disclosure of Invention

The invention aims to overcome the technical defects and provide a preparation method of a novel non-hardening coupling iron-carbon micro-electrolysis filler, which permanently and thoroughly solves the hardening and passivation of the iron-carbon micro-electrolysis filler.

In order to solve the technical problems, the technical scheme provided by the invention is as follows: a preparation method of a novel non-hardening coupling iron-carbon micro-electrolysis filler comprises the following steps:

step 1: screening iron ore powder or iron oxide scales with the iron content of 30-90% by a magnetic separator, crushing and screening by a crusher to 10-200 meshes, and storing for later use;

step 2: putting the iron powder sieved in the step 1 into the center of a refractory container, putting a reducing agent prepared by anthracite and quicklime according to the ratio of 8: 1-7: 2 around the iron powder, sealing the refractory container, putting the refractory container into a reducing furnace, roasting and reducing the refractory container for 28-52 hours at the temperature of 1150-1360 ℃, cooling the refractory container, taking out the reducing agent, taking out the residual reduced iron powder Fe, and storing the residual reduced iron powder Fe for later use;

and step 3: taking 50-90% of Fe, 5-20% of C, 0.012-1.5% of AL, 0.00136-0.2% of Ti, 0.1-2.89% of Cu, 0.0026-0.3% of Mn and 0.002-0.013% of Ag in the step 2, uniformly mixing, putting into a refractory container, putting into a sintering furnace, 1260 and 1458 ℃ for sintering for 2-16 hours to integrate the materials into a solid phase, cooling, taking out, crushing by a crusher, grinding into a grinder with a mesh size of 1-2000 or grinding into nano-grade comprehensive metal powder, and storing for later use;

and 4, step 4: respectively loading 15-80% of plant starch, 1-15% of plant cellulose, 0.3-8.5% of humic acid and 20-65% of water into a mixing machine bin, and fully mixing by a mixing machine to obtain a paste mixed solution for later use;

and 5: taking 100 parts of the comprehensive metal powder in the step 3, putting the comprehensive metal powder into a mixing machine bin filled with the pasty mixed liquid in the step 4, fully and uniformly mixing until the surface of each fine comprehensive metal powder particle is fully coated with slurry, drying the mixture at 260 ℃ in a drying machine, cooling and taking out the mixture, putting the mixture into a refractory container, putting the refractory container into a high-temperature sintering furnace, carrying out anaerobic roasting at 965 ℃ for 6-11 hours to carbonize the surface of the coated slurry of the comprehensive metal powder, opening micropores through high-temperature steam activation, and carrying out anaerobic cooling and discharging the mixture out of the furnace for later use;

step 6: 20-70% of porcelain powder, 7-11% of pulverized coal slag, 5-10% of limestone, 0.5-1.5% of iron ore powder and 5-20% of gypsum are dried at 260 ℃ through 100-;

and 7: and (3) adding 20-90 parts of the comprehensive metal powder obtained in the step (5) into 10-80 parts of the coupling agent obtained in the step (6), sending the mixture into a stirrer for fully stirring and mixing for 10-30 minutes, uniformly adding 5-16% of water, fully stirring and reacting for 15-45 minutes to prepare a comprehensive wet material, sending the comprehensive wet material into a high-pressure forming device for press forming, stacking and aging for 12-48 hours, spraying 30-40% of water for aging for 72 hours, sending the comprehensive wet material into a microwave high-temperature furnace for drying and sintering at 960 ℃ for 8-16 hours, cooling to below 30 ℃, discharging, and screening to obtain the novel non-hardened coupling iron-carbon micro-electrolysis filler with the grey appearance.

Compared with the prior art, the invention has the advantages that: the prepared non-hardening coupling iron-carbon micro-electrolysis filler permanently solves the problem of hardening and passivation of the iron-carbon filler, utilizes the reaction principle of a primary battery to treat various sewage with high concentration, high toxicity, high chroma, high heavy metal and difficult biochemical treatment, particularly has very high treatment effect on COD, chroma and heavy metal of the sewage, improves the B \ C ratio of the sewage, greatly improves the biodegradability of the sewage, and creates favorable conditions for the standard discharge of the sewage; the novel non-hardening coupling iron-carbon micro-electrolysis filler is widely applied to the treatment of various refractory, high-toxicity and difficult-biochemical industrial wastewater, upgrading and modification and reclaimed water recycling engineering, such as chemical engineering, medical intermediates, electroplating, printing and dyeing, pharmacy, pesticides, landfill leachate, dyes, chemical fibers, tanning, slaughtering, coking, comprehensive sewage treatment in a park and the like.

Detailed Description

Example 1:

a preparation method of a novel non-hardening coupling iron-carbon micro-electrolysis filler comprises the following steps:

step 1: screening iron ore powder or iron oxide scales with iron content of 88% by a magnetic separator, crushing and screening by a crusher to 200 meshes, and storing for later use;

step 2: putting the iron powder screened out in the step 1 into the center of a refractory container, filling a reducing agent prepared by anthracite and quicklime according to a ratio of 8:1 around the iron powder, sealing the refractory container, putting the refractory container into a reducing furnace, roasting and reducing the refractory container at 1260 ℃ for 35 hours, cooling, taking out the reducing agent, taking out the residual reduced iron powder (Fe), and storing for later use;

and step 3: taking 86.558% of Fe, 11% of C, 1.14% of AL, 0.02% of Ti, 1.25% of Cu1, 0.03% of Mn and 0.002% of Ag in the step 2, uniformly mixing, putting into a refractory container, putting into a sintering furnace, sintering at 1438 ℃ for 9 hours to enable the materials to be integrally combined in a solid phase, cooling, taking out, crushing by a crusher, grinding by a grinder to obtain nano-level comprehensive metal powder, and storing for later use;

and 4, step 4: respectively filling 28% of plant starch, 6% of plant cellulose, 1.5% of humic acid and 64.5% of water into a mixing machine bin, and fully mixing the mixture into a paste mixed solution for later use by a mixing machine;

and 5: taking 100 parts of the comprehensive metal powder obtained in the step (3), putting the comprehensive metal powder into a mixing machine bin filled with the pasty mixed liquid obtained in the step (4), fully and uniformly mixing until the surface of each fine comprehensive metal powder particle is fully coated with slurry, drying the fine comprehensive metal powder particle at 210 ℃ in a dryer, cooling and taking out the fine comprehensive metal powder particle, putting the fine comprehensive metal powder particle into a refractory container, putting the refractory container into a high-temperature sintering furnace, carrying out anaerobic roasting at 915 ℃ for 8 hours to carbonize the surface of the coated slurry of the comprehensive metal powder, activating by high-temperature;

step 6: 60% of porcelain powder, 11% of coal powder slag, 10% of limestone, 1.5% of iron ore powder and 18.5% of gypsum are taken, dried at 115 ℃, respectively crushed and ground into 260 meshes by a crusher, fully and uniformly mixed, sent into a dry sintering furnace for calcination at 1450 ℃, cooled and taken out of the furnace to prepare a coupling agent;

and 7: and (3) adding 75 parts of the comprehensive metal powder obtained in the step (5) into 25 parts of the coupling agent obtained in the step (6), feeding the mixture into a stirrer, fully stirring and mixing for 25 minutes, uniformly adding 11.8% of water, fully stirring and reacting for 45 minutes to prepare a comprehensive wet material conveying belt, feeding the comprehensive wet material conveying belt into high-pressure forming equipment, press-forming, stacking and aging for 48 hours, spraying water for 40%, aging for 72 hours, feeding the comprehensive wet material conveying belt into a microwave high-temperature furnace for drying and sintering at 960 ℃ for 16 hours, cooling to below 30 ℃, discharging, and screening to obtain the novel non-hardened coupling iron-carbon.

The novel non-hardening coupling iron-carbon micro-electrolysis filler produced and prepared by using the raw materials and the data is detected by Guangzhou Zhongzhou detection technology service Co., Ltd in 2020, 04 and 01 days, and the detection report is numbered: HG200401-49, the detection results are as follows:

detecting items	Detection method	Unit of	The result of the detection
				Specific surface area	GB/7702.20-2008	㎡/g	1.80
Specific gravity of	GB/T7702.4-1997	g/L	1525
				Bulk density	GB/T30202.1-2013	g/L	1506
Void fraction	GB/T14684-2011	％	60.2

The novel non-hardening coupling iron-carbon micro-electrolysis filler prepared by using the raw materials and the data has the advantages that the COD treatment rate of the percolate wastewater in the domestic garbage landfill is up to 80.05 percent, the data rate is better, and the data is as follows:

example 2:

step 1: screening iron ore powder or iron oxide scales with iron content of 90% by a magnetic separator, crushing and screening by a crusher to 150 meshes, and storing for later use;

step 2: loading the iron powder sieved in the step 1 into the center of a refractory container, loading a reducing agent prepared by anthracite and quicklime according to a ratio of 7:2 around the iron powder, sealing the refractory container, loading the refractory container into a reducing furnace, roasting and reducing the refractory container for 30 to 52 hours at a temperature of 1150 to 1360 ℃, cooling, taking out the reducing agent, taking out the rest reduced iron powder (Fe), and storing for later use;

and step 3: taking 92.2182% of Fe, 6.6% of C, 0.07% of AL, 0.18% of Ti, 0.9% of Cu0.9% of Mn and 0.03% of Ag, uniformly mixing, putting into a refractory container, putting into a sintering furnace, sintering at 1438 ℃ for 9 hours to enable the materials to be integrally combined in a solid phase, cooling, taking out, crushing by a crusher, grinding into comprehensive metal powder of 290 meshes by a grinder, and storing for later use;

and 4, step 4: respectively filling 38% of plant starch, 4% of plant cellulose, 0.8% of humic acid and 57.2% of water into a mixing machine bin, and fully mixing the mixture into a paste mixed solution for later use by a mixing machine;

and 5: taking 100 parts of the comprehensive metal powder obtained in the step (3), putting the comprehensive metal powder into a mixing machine bin filled with the pasty mixed liquid obtained in the step (4), fully and uniformly mixing until the surface of each fine comprehensive metal powder particle is fully coated with slurry, drying the fine comprehensive metal powder particle at 210 ℃ in a dryer, cooling and taking out the fine comprehensive metal powder particle, putting the fine comprehensive metal powder particle into a refractory container, putting the refractory container into a high-temperature sintering furnace, carrying out anaerobic roasting at 915 ℃ for 9.5 hours to carbonize the surface of the coated slurry of the comprehensive metal powder, activating by high-temperature;

step 6: taking 70% of porcelain powder, 7% of coal powder slag, 6.5% of limestone, 1% of iron ore powder and 15.5% of gypsum, drying at 115 ℃, respectively crushing and grinding into 300 meshes by using a crusher, fully and uniformly mixing, feeding into a dry sintering furnace, calcining at 1360 ℃, cooling and discharging to prepare a coupling agent;

and 7: and (3) adding 79 parts of the comprehensive metal powder obtained in the step (5) into 21 parts of the coupling agent obtained in the step (6), feeding the mixture into a stirrer, fully stirring and mixing for 25 minutes, uniformly adding 7.8% of water, fully stirring and reacting for 45 minutes to prepare a comprehensive wet material conveying belt, feeding the comprehensive wet material conveying belt into high-pressure forming equipment, press-forming, stacking and aging for 48 hours, spraying water for 35%, aging for 72 hours, feeding the comprehensive wet material conveying belt into a microwave high-temperature furnace for drying and sintering at 960 ℃ for 13 hours, cooling to below 30 ℃, discharging, and screening to obtain the novel non-hardened coupling iron-carbon.

The novel non-hardening coupling iron-carbon micro-electrolysis filler prepared by using the raw materials and the data has a high COD treatment rate of 66% in the treatment of the cephalosporin medical intermediate wastewater, and has better treatment data rates, wherein the data is as follows:

example 3:

step 1: screening iron ore powder or iron oxide scales with iron content of 80% by a magnetic separator, crushing and screening by a crusher to 100 meshes, and storing for later use;

step 2: putting the iron powder sieved in the step 1 into the center of a refractory container, filling a reducing agent prepared by anthracite and quicklime according to a ratio of 7:2 around the iron powder, sealing the refractory container, putting the refractory container into a reducing furnace, roasting and reducing the refractory container at 1290 ℃ for 28 hours, cooling, taking out the reducing agent, taking out the residual reduced iron powder Fe, and storing for later use;

and step 3: taking 77.72% of Fe, 20% of C, 0.15% of AL, 0.01% of Ti, 2.1% of Cu2, 0.018% of Mn and 0.002% of Ag in the step 2, uniformly mixing, putting into a refractory container, putting into a sintering furnace, sintering at 430 ℃ for 11 hours to integrally combine the materials in a solid phase, cooling, taking out, crushing by a crusher, grinding into comprehensive metal powder of 450 meshes by a grinder, and storing for later use;

and 4, step 4: respectively filling 31% of plant starch, 15% of plant cellulose, 1.36% of humic acid and 52.64% of water into a mixing machine bin, and fully mixing the mixture into a paste mixed solution for later use;

and 5: taking 100 parts of the comprehensive metal powder obtained in the step 3, putting the comprehensive metal powder into a mixing machine bin filled with the pasty mixed liquid obtained in the step 4, fully and uniformly mixing until the surface of each fine comprehensive metal powder particle is fully coated with slurry, drying the fine comprehensive metal powder particle at 190 ℃ in a dryer, cooling and taking out the fine comprehensive metal powder particle, putting the fine comprehensive metal powder particle into a refractory container, putting the refractory container into a high-temperature sintering furnace, performing anaerobic roasting at 965 ℃ for 10.5 hours to carbonize the surface of the coated slurry of the comprehensive metal powder, activating by high-temperature steam to open;

step 6: taking 63% of porcelain powder, 8.3% of pulverized coal slag, 9.5% of limestone, 1.2% of iron ore powder and 18.5% of gypsum, drying at 115 ℃, respectively crushing and grinding into 360 meshes by using a crusher, fully and uniformly mixing, feeding into a dry sintering furnace for calcination at 1350 ℃ and 1450 ℃, cooling and taking out of the furnace to prepare a coupling agent;

and 7: and (3) adding 59 parts of the comprehensive metal powder obtained in the step (5) into 41 parts of the coupling agent obtained in the step (6), feeding the mixture into a stirrer, fully stirring and mixing for 25 minutes, uniformly adding 5.78% of water, fully stirring and reacting for 45 minutes to prepare a comprehensive wet material conveying belt, feeding the comprehensive wet material conveying belt into high-pressure forming equipment, press-forming, stacking and aging for 48 hours, spraying water for 40%, aging for 72 hours, feeding the comprehensive wet material conveying belt into a microwave high-temperature furnace for drying and sintering at 960 ℃ for 16 hours, cooling to below 30 ℃, discharging, and screening to obtain the novel non-hardened coupling iron-carbon.

The novel non-hardening coupling iron-carbon micro-electrolysis filler prepared by using the raw materials and the data has a COD treatment rate of 89 percent and better treatment data rate when used for treating fine chemical wastewater, and the data is as follows:

the invention and the embodiments thereof have been described above, without limitation, and those skilled in the art will be able to devise similar methods and embodiments without departing from the spirit and scope of the invention.

Claims

1. A preparation method of a novel non-hardening coupling iron-carbon micro-electrolysis filler is characterized by comprising the following steps:

and step 3: taking 50-93% of Fe, 5-20% of C, 0.012-1.5% of AL, 0.00136-0.2% of Ti, 0.1-2.89% of Cu, 0.0026-0.3% of Mn and 0.002-0.013% of Ag in the step 2, uniformly mixing, putting into a refractory container, putting into a sintering furnace, 1260 and 1458 ℃, sintering for 2-16 hours to enable the materials to be integrally and solidly combined, taking out after cooling, crushing by a crusher, grinding into comprehensive metal powder of 1-2000 meshes or nano-grade by a grinder, and storing for later use;