CN102909363A - Iron-base alloy compound material, preparation method thereof and method for disposing petroleum drilling wastewater - Google Patents
Iron-base alloy compound material, preparation method thereof and method for disposing petroleum drilling wastewater Download PDFInfo
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- CN102909363A CN102909363A CN2012103978479A CN201210397847A CN102909363A CN 102909363 A CN102909363 A CN 102909363A CN 2012103978479 A CN2012103978479 A CN 2012103978479A CN 201210397847 A CN201210397847 A CN 201210397847A CN 102909363 A CN102909363 A CN 102909363A
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Abstract
The invention discloses an iron-base alloy compound material. The iron-base alloy compound material is formed by uniformly mixing scrap iron of 90%-65% by weight and iron-base amorphous alloy scraps of 10%-35% by weight, wherein the carbon content of the scrap iron is 1%-3%; the iron-base amorphous alloy scraps include the following components in atomic percents: iron of 60%-82%, Si of 7%-12% and B of 11%-13%. The invention also provides a preparation method of the iron-base alloy compound material. The preparation method comprises the steps of: (1) preparing the scrap iron; (2) preparing the iron-base amorphous alloy; and (3) uniformly mixing the scrap iron alloy with the amorphous alloy metal alloy according to the proportion. The invention provides a method for disposing petroleum drilling wastewater by using the iron-base alloy compound material. The method comprises the steps of filling the iron-base alloy compound material in a container; filling the petroleum drilling wastewater into a tank body; and inflating the tank body through an air blower to perform an aeration treatment. The iron-base alloy compound material, the preparation method thereof and the method for disposing the petroleum drilling wastewater, disclosed by the invention, has the advantages of a simple process, cyclic utilization, no pollution, good treatment effects and convenience for operation.
Description
Technical field
The present invention relates to a kind of ferrous metals composite, its preparation method of processing oil drilling waste, and process the method for oil drilling waste, belong to water treatment and technical field of metal material preparation.
Background technology
Along with industrial expansion, the pollution level of water is on the rise.As a class of waste water, oil drilling waste is the more unmanageable waste water of field of waste water treatment one class, and this type of contaminated wastewater is high, and viscosity is large, and complicated component is the difficult problem of demanding urgently breaking off relations that oil drilling industry and environmental protection industry (epi) face.The cost that oil drilling waste is processed is higher, and intractability is large, and traditional method is difficult to be processed to reinjection standard, or processing cost is very high.If but do not process direct discharging, waste water then not only could pollute near the soil the oil field, and can strengthen the oil field reinjection water use amount and strengthen cost.Be accompanied by national increasing to the monitoring of environment dynamics and enterprise to the raising of environmental consciousness, to the also thereupon increase of processing requirements of oil drilling waste.At present the method for oil drilling waste is mainly take natural subsidence and coagulant precipitation as main, and is accompanied by Physical, chemical method, bioanalysis etc.The iron-carbon micro-electrolysis method is with a kind of widely used method, and conventional method is that iron carbon is joined in the waste water according to a certain percentage, utilizes the potential difference between the iron carbon, forms small galvanic cell, and the pollutant in the water is decomposed.
But the iron-carbon micro-electrolysis method has certain limitation, and is lower such as iron-holder, during reaction in the water dissolved iron ion concentration lower, poor processing effect; Easily harden, material needs often to change; Filler stops up easily, is difficult for dredging, and stability of material is bad, and later maintenance is inconvenient.
Summary of the invention
The objective of the invention is for overcoming above-mentioned the deficiencies in the prior art, a kind of ferrous metals electrolysis material and treatment process of processing oil drilling waste is provided.This material is coupled ferrous metals non-crystalline material and iron filings, utilizes both sides' characteristics, and treatment effect is enhanced, and remedies the deficiency of existing iron-carbon micro-electrolytic material, and effectively avoids a series of difficult problems in engineering is used.
For achieving the above object, the present invention adopts following technical proposals:
A kind of ferrous alloy composite, be that the iron filings of 90%-65% and percentage by weight are that 10% ~ 35% Fe-based amorphous alloy chip mixes and forms by percentage by weight, the phosphorus content of described iron filings is 1% ~ 3%, and described Fe-based amorphous alloy comprises the following component by atomic percent: 60% ~ 82% iron, 7% ~ 12% Si and 11% ~ 13% B.
In this technical scheme, add the elements such as Si, B, make its easier amorphous metallic material that is processed as.
The rare earth magnesium that also comprises 0＜percentage by weight≤0.1% in the described iron filings.Percentage by weight is the percentage that accounts for its made iron filings.Described rare earth magnesium refers to contain the magnesium alloy of rare earth element, and the purpose of adding is to improve follow-up catalytic effect.
Described iron filings are the helical metal chip of diameter 0.5-1.5cm.Be preferably the helical metal chip of 1cm.
The amorphous metal chip that described Fe-based amorphous alloy chip is diameter 0.5-1.5cm, the amorphous metal chip of preferred 1cm.Described amorphous metal chip is that thickness is the sheet shaped piece of 20 ~ 100 μ m.Width is 5 ~ 10mm.
This Fe-based amorphous alloy chip can prepare in the following manner: by rapid solidification equipment ferrous alloy being treated to thickness is 20 ~ 100 μ m, and width is 5 ~ 10mm, then is treated to the amorphous metal chip of diameter 1cm by disintegrating apparatus.
Preferably, the weight ratio of described iron filings and Fe-based amorphous alloy chip is 4:1, in the described Fe-based amorphous alloy chip by atomic percent iron 78%, silicon 9%, boron 13%.Perhaps the weight ratio of described iron filings and Fe-based amorphous alloy chip is 5:1, in the described Fe-based amorphous alloy chip by atomic percent iron 77%, silicon 11%, boron 12%.
The present invention also provides above-mentioned ferrous alloy composite manufacture method, may further comprise the steps:
(1) preparation of iron filings: choose ingot iron, be formulated as the ingot iron of phosphorus content 1%-3% with carbon dust, and make iron filings;
(1) preparation of Fe-based amorphous alloy: (a) according to selected alloying component, carry out the weighing proportioning, the alloy of refining selected components under the protection of inert gas; (b) utilize rapid solidification equipment, the alloy of refining is carried out remelting under the protection of inert gas, when composition melts when even, utilize instantaneous differential pressure that rapid solidification is carried out in the molten metal splash to the running roller and process and obtain amorphous ribbon; (c) utilize disintegrating apparatus that amorphous ribbon is pulverized and be the amorphous metal fragment of diameter less than 1cm;
(3) iron filings alloy and amorphous metal alloy are proportionally mixed and get final product.
The rare earth magnesium that in the preparation of ingot iron, also adds 0＜percentage by weight≤0.1% in the step (1).With their high temperature melting of ingot iron, carbon dust and rare earth magnesium, mix, and be cast into ingot iron.
Iron filings are to be processed into the spiral bits shape metal fragment that diameter is 0.5-1.5cm.Be preferably 1cm.
The invention provides the method for the processing oil drilling waste of this ferrous alloy composite, may further comprise the steps: the ferrous alloy composite is filled in container, oil drilling waste is injected in the tank body, carries out Air Exposure by air blast inflation in the tank body.
In the method, in order to improve treatment effect and speed, the pH value can be adjusted into 3 ~ 6 and carry out again Air Exposure.Also can add hydrogen peroxide according to the amount of hydrogen peroxide ratio wastewater volume 1:1000 ~ 1:200 to improve treatment effect.
Operation principle of the present invention is: Fe-based amorphous alloy is because its atomic arrangement is in the coordination undersaturated condition of height, make it that more catalytic active center be arranged, and its activity of Fe-based amorphous alloy is higher than common iron-based crystalline material, and this strengthens its catalytic capability greatly.Fe-based amorphous alloy and iron filings alloy efficient coupling make material itself have very strong catalytic capability, produce the higher active group of more concentration in the processing procedure, and the iron content in the electrolysis material is higher simultaneously, and both interactions have improved degradation effect greatly.
In description of the invention, ferrous metals electrolysis material, ferrous metals composite all represent the prepared ferrous alloy composite of the present invention.
The invention has the beneficial effects as follows, the present invention has overcome traditional high-efficient treatment method complex process, operating cost is high, the shortcomings such as common electrolysis material easily hardens, weak effect, be a kind of preparation technology of having simple, pollution-free, be difficult for to stop up, operating cost is low, activity is high, treatment effect is good, safeguards simple petroleum wastewater electrolysis material and treatment process.The present invention can be used for the processing of petroleum wastewater process field and other used water difficult to degradate.
The specific embodiment
The present invention will be further elaborated below by instantiation, should be noted that following explanation only is in order to explain the present invention, its content not to be limited.
Embodiment 1:
One. Fe-based amorphous material preparation
(1) at first takes by weighing raw material by the atomic percent of iron 78%, silicon 9%, boron 13%;
(2) get the glass tube that an end seals, its bottom and side have a passage; Load weighted raw material is put into glass tube bottom uniformly, then use rubber stopper with the protective gas pipeline glass tube mouth of pipe jam-pack, to carry out the gas shield melting and to prevent that gas from overflowing from the upper end; Glass tube is placed on the cuvette holder of smelting furnace, makes raw material in the glass tube just in time be in the induction coil place of smelting furnace, and the protective gas pipeline of rubber stopper is connected on the argon gas source;
(3) open protective gas, and regulate air-flow to 0.1 ~ 0.15MPa, glass tube inside is in the argon shield atmosphere, glass tube bottom and lateral aperture place have slight air-flow to flow out;
(4) open the heater switch of smelting furnace, make its full and uniform reaction 3 ~ 5 minutes at 1000 ~ 1200 ℃, then stopped heating makes its naturally cooling under the gas shield state, obtains alloy pig; Behind the polishing alloy pig surface, be cut to the sample that gets rid of with usefulness;
(5) get rid of band: adopt the high frequency remelting to get rid of carry sample, the expulsion pressure of melt is 0.1 ~ 0.2MPa, and the injection temperation of melt is 950 ~ 1100 ℃; Getting rid of band carries out under argon shield;
(6) carrying out material processed, is the sheet shaped piece of diameter 1cm with Fe-based amorphous material disintegrating by pulverizer.
Two. the preparation of ferrous metals alloy material
At first choose ingot iron, the percentage by weight that accounts for prepared ingot iron with an amount of carbon dust and 0.05%() to be formulated as phosphorus content be 2% ingot iron to rare earth magnesium, by lathe its car become spiral bits shape thing about diameter 1cm.
Three. the filling of composite
With iron filings alloy and amorphous metal alloy according to the 4:1(weight ratio) ratio mix, notice that iron filings and amorphous metallic alloy carry out mixed packing, and each layer metal material is evenly distributed in the container in mixed process.
Four. treatment process
Iron filings and non-crystalline material are loaded according to above-mentioned designation method, and subsequently with in the waste water injecting reactor, regulating the pH value is 3 ~ 5, carries out Air Exposure 2 ~ 3 hours by air blast.
Five. treatment effect
By testing in the engineering, process according to the method described above oil drilling waste, the COD of test oil drilling waste is 43500mg/l before processing.During test 50 times of this oil drilling waste dilutions are processed by the method for standard " the mensuration rapid-digestion AAS HJ/T 399-2007 of water chemical oxygen demand " (2007-12-07 issue) record afterwards.After tested, its treatment effect can be removed COD and reach 37%, and the iron filings that the adding total amount equates are processed the waste water with sample ingredient under the same conditions, and removal effect is 26%.
Embodiment 2:
One. Fe-based amorphous material preparation
(1) at first takes by weighing raw material by the atomic percent of iron 77%, silicon 11%, boron 12%;
(2) get the glass tube that an end seals, its bottom and side have a passage; Load weighted raw material is put into glass tube bottom uniformly, then use rubber stopper with the protective gas pipeline glass tube mouth of pipe jam-pack, to carry out the gas shield melting and to prevent that gas from overflowing from the upper end; Glass tube is placed on the cuvette holder of smelting furnace, makes raw material in the glass tube just in time be in the induction coil place of smelting furnace, and the protective gas pipeline of rubber stopper is connected on the argon gas source;
(3) open protective gas, and regulate air-flow to 0.1 ~ 0.15MPa, glass tube inside is in the argon shield atmosphere, glass tube bottom and lateral aperture place have slight air-flow to flow out;
(4) open the heater switch of smelting furnace, make its full and uniform reaction 3 ~ 5 minutes at 1000 ~ 1200 ℃, then stopped heating makes its naturally cooling under the gas shield state, obtains alloy pig; Behind the polishing alloy pig surface, be cut to the sample that gets rid of with usefulness;
(5) get rid of band: adopt the high frequency remelting to get rid of carry sample, the expulsion pressure of melt is 0.1 ~ 0.2MPa, and the injection temperation of melt is 950 ~ 1100 ℃; Getting rid of band carries out under argon shield;
(6) carrying out material processed, is the sheet shaped piece of diameter 1cm with Fe-based amorphous material disintegrating by pulverizer.
Two. the preparation of ferrous metals alloy material
At first choose ingot iron, the percentage by weight that accounts for prepared ingot iron with an amount of carbon dust and 0.08%() rare earth magnesium is formulated as the ingot iron of phosphorus content 3%, by lathe its car become spiral bits shape thing about diameter 1cm.
Three. the filling of composite
With iron filings alloy and amorphous metal alloy according to the 5:1(weight ratio) ratio mix, notice that iron filings and amorphous metallic alloy carry out mixed packing, and each layer metal material is evenly distributed in the container in mixed process.
Four. treatment process
Iron filings and non-crystalline material are loaded according to above-mentioned designation method, and subsequently with in the waste water injecting reactor, regulating the pH value is 3 ~ 5, and adds hydrogen peroxide according to the amount of waste water and hydrogen peroxide 1000:1, carries out Air Exposure 2 ~ 3 hours by air blast.
Five. treatment effect
By testing in the engineering, oil drilling waste in the Processing Example 1 adopts method of testing among the embodiment 1 according to the method described above, and its treatment effect can be removed COD and reach 48%, and the iron filings that the adding total amount equates are processed the waste water with sample ingredient under the same conditions, and removal effect is 32%.
Claims (10)
1. ferrous alloy composite, it is characterized in that, be that the iron filings of 90%-65% and percentage by weight are that 10% ~ 35% Fe-based amorphous alloy chip mixes and forms by percentage by weight, the phosphorus content of described iron filings is 1% ~ 3%, and described Fe-based amorphous alloy comprises the following component by atomic percent: 60% ~ 90% iron, 7% ~ 12% silicon and 11% ~ 13% boron.
2. ferrous alloy composite as claimed in claim 1 is characterized in that, also comprises the rare earth magnesium of 0＜percentage by weight≤0.1% in the described iron filings.
3. ferrous alloy composite as claimed in claim 1 is characterized in that, described iron filings are the helical metal chip of diameter 0.5-1.5cm.
4. ferrous alloy composite as claimed in claim 1 is characterized in that, the amorphous metal chip that described Fe-based amorphous alloy chip is diameter 0.5-1.5cm.
5. ferrous alloy composite manufacture method claimed in claim 1 is characterized in that, may further comprise the steps:
(1) preparation of iron filings: choose ingot iron, be formulated as the ingot iron of phosphorus content 1%-3% with carbon dust, and make iron filings;
(2) preparation of Fe-based amorphous alloy: (a) according to selected alloying component, carry out the weighing proportioning, the alloy of refining selected components under the protection of inert gas; (b) utilize rapid solidification equipment, the alloy of refining is carried out remelting under the protection of inert gas, when composition melts when even, utilize instantaneous differential pressure that rapid solidification is carried out in the molten metal splash to the running roller and process and obtain amorphous ribbon; (c) utilize disintegrating apparatus that amorphous ribbon is pulverized and be the amorphous metal fragment of diameter less than 1cm;
(3) iron filings alloy and amorphous metal alloy are proportionally mixed and get final product.
6. preparation method as claimed in claim 5 is characterized in that, also adds the rare earth magnesium of 0＜percentage by weight≤0.1% in the step (1) in the preparation of ingot iron.
7. preparation method as claimed in claim 5 is characterized in that, iron filings are to be processed into the spiral bits shape metal fragment that diameter is 0.5-1.5cm in the step (1).
8. the method for the processing oil drilling waste of each described ferrous alloy composite of claim 1-4, it is characterized in that, may further comprise the steps: the ferrous alloy composite is filled in container, oil drilling waste is injected in the tank body, carries out Air Exposure by air blast inflation in the tank body.
9. the method for processing oil drilling waste as claimed in claim 8 is characterized in that, the pH value with oil drilling waste before the Air Exposure is adjusted into 3 ~ 6.
10. the method for processing oil drilling waste as claimed in claim 8 is characterized in that, the amount according to hydrogen peroxide ratio wastewater volume 1:1000 ~ 1:200 before the Air Exposure adds hydrogen peroxide.
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| CN105177477A (en) * | 2015-09-03 | 2015-12-23 | 王文姣 | Efficient sewage treatment equipment |
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| CN106006916A (en) * | 2016-07-18 | 2016-10-12 | 中国科学院金属研究所 | Method for degradation of coking wastewater by utilizing Fe-base amorphous alloy |
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| CN105174380A (en) * | 2015-09-03 | 2015-12-23 | 王文姣 | Sewage treatment equipment |
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| US11970761B2 (en) | 2017-12-21 | 2024-04-30 | Qingdao Yunlu Advanced Materials Technology Co., Ltd. | Iron-based amorphous alloy and preparation method therefor |
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