CN102909363B - 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
- Publication number
- CN102909363B CN102909363B CN201210397847.9A CN201210397847A CN102909363B CN 102909363 B CN102909363 B CN 102909363B CN 201210397847 A CN201210397847 A CN 201210397847A CN 102909363 B CN102909363 B CN 102909363B
- Authority
- CN
- China
- Prior art keywords
- iron
- alloy
- preparation
- iron filings
- compound material
- 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.)
- Expired - Fee Related
Links
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
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 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 discharge, waste water not only could pollute near soil oil field, and can strengthen oil field reinjection water use amount and strengthen cost.Be accompanied by country's raising to environmental consciousness to the increasing of monitoring of environment dynamics and enterprise, the processing requirements of oil drilling waste is also increased thereupon.At present the method for oil drilling waste mainly be take natural subsidence and coagulant precipitation as main, and is accompanied by Physical, chemical method, bioanalysis etc.Iron-carbon micro-electrolysis method is with a kind of widely used method, and conventional method is that iron carbon is joined in waste water according to a certain percentage, utilizes the potential difference between iron carbon, forms small galvanic cell, and the pollutant in water is decomposed.
But iron-carbon micro-electrolysis method has certain limitation, such as iron-holder is lower, during reaction, in water, dissolved iron ion concentration is lower, poor processing effect; Easily harden, material needs often to change; Filler easily stops up, and is difficult for dredging, and stability of material is bad, and later maintenance is inconvenient.
Summary of the invention
The object 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' feature, and treatment effect is enhanced, and makes up the deficiency of existing iron-carbon micro-electrolytic material, and effectively avoids a series of difficult problems in engineering application.
For achieving the above object, the present invention adopts following technical proposals:
A kind of ferrous alloy composite, the iron filings that are 90%-65% by percentage by weight and percentage by weight are that 10% ~ 35% Fe-based amorphous alloy chip mixes and forms, 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 it more easily be processed as amorphous metallic material.
In described iron filings, also comprise the rare earth magnesium of 0 < percentage by weight≤0.1%.Percentage by weight is the percentage that accounts for its made iron filings.Described rare earth magnesium refers to the magnesium alloy that contains rare earth element, and the object 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, preferably the amorphous metal chip of 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 be prepared 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 by disintegrating apparatus, is treated to the amorphous metal chip of diameter 1cm.
Preferably, the weight ratio of described iron filings and Fe-based amorphous alloy chip is 4:1, in described Fe-based amorphous alloy chip by atomic percent iron 78%, silicon 9%, boron 13%.Or the weight ratio of described iron filings and Fe-based amorphous alloy chip is 5:1, in described Fe-based amorphous alloy chip by atomic percent iron 77%, silicon 11%, boron 12%.
The present invention also provides the preparation method of above-mentioned ferrous alloy composite, comprises the following 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, weigh proportioning, refine the alloy of selected components under the protection of inert gas; (b) utilize rapid solidification equipment, the alloy of refining is carried out under the protection of inert gas to remelting, when composition melts when even, utilize instantaneous differential pressure that molten metal splash is processed and obtained amorphous ribbon to carrying out rapid solidification on running roller; (c) utilize disintegrating apparatus amorphous ribbon to be pulverized to the amorphous metal fragment that is less than 1cm for diameter;
(3) iron filings alloy is proportionally mixed and be get final product with amorphous metal alloy.
In step (1), in the preparation of ingot iron, also add the rare earth magnesium of 0 < percentage by weight≤0.1%.By 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, comprise the following steps: ferrous alloy composite is filled in container, oil drilling waste is injected in tank body, by air blast, to inflation in tank body, carries out Air Exposure.
In the method, in order to improve treatment effect and speed, pH value can be adjusted into 3 ~ 6 and carry out again Air Exposure.Also can add hydrogen peroxide to improve treatment effect according to the amount of hydrogen peroxide ratio wastewater volume 1:1000 ~ 1:200.
Operation principle of the present invention is: Fe-based amorphous alloy is due to the coordination undersaturated condition of its atomic arrangement in height, make it have more catalytic active center, and its activity of Fe-based amorphous alloy is higher than common iron-based crystalline material, this strengthens its catalytic capability greatly.Fe-based amorphous alloy and iron filings alloy efficient coupling, make material itself have very strong catalytic capability, produces the higher active group of more concentration in processing procedure, and the iron content in 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 ferrous alloy composite that the present invention is prepared.
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 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
Below by instantiation, the present invention will be further elaborated, should be noted that following explanation is only in order to explain the present invention, does not limit its content.
Embodiment 1:
One. the preparation of Fe-based amorphous material
(1) first by the atomic percent of iron 78%, silicon 9%, boron 13%, take raw material;
(2) get the glass tube of one end sealing, its bottom and side have a passage; Load weighted raw material is put into glass tube bottom uniformly, then use rubber stopper with protective gas pipeline glass tube mouth of pipe jam-pack, to carry out gas shield melting and to prevent that gas from overflowing from upper end; Glass tube is placed on the cuvette holder of smelting furnace, makes the just in time induction coil place in smelting furnace of raw material in glass tube, and the protective gas pipeline of rubber stopper is connected on argon gas source;
(3) open protective gas, and regulate air-flow to 0.1 ~ 0.15MPa, make glass tube inside in 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, at 1000 ~ 1200 ℃, make its full and uniform reaction 3 ~ 5 minutes, then stop heating, make its cooling naturally under gas shield state, obtain alloy pig; Behind polishing alloy pig surface, be cut to the sample getting rid of with use;
(5) get rid of band: adopt 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 ℃; Get rid of band carries out under argon shield;
(6) carrying out material processed, is the sheet shaped piece of diameter 1cm by Fe-based amorphous material disintegrating by pulverizer.
Two. the preparation of ferrous metals alloy material
First choose ingot iron, the percentage by weight that accounts for prepared ingot iron with appropriate carbon dust and 0.05%() to be formulated as phosphorus content be 2% ingot iron to rare earth magnesium, by lathe, its car become to the spiral bits shape thing of diameter 1cm left and right.
Three. the filling of composite
By iron filings alloy with amorphous metal alloy according to 4:1(weight ratio) ratio mix, notice that, in mixed process, iron filings and amorphous metallic alloy carry out mixed packing, and each layer of metal material is evenly distributed in container.
Four. treatment process
Iron filings and non-crystalline material are loaded according to above-mentioned designation method, and subsequently by waste water injecting reactor, regulating pH value is 3 ~ 5, by air blast, carries out Air Exposure 2 ~ 3 hours.
Five. treatment effect
By testing in engineering, process according to the method described above oil drilling waste, before processing, the COD of test oil drilling waste is 43500mg/l.During test, 50 times of methods of recording by the mensuration rapid-digestion AAS HJ/T 399-2007 > > (2007-12-07 issue) of standard < < water chemical oxygen demand afterwards of this oil drilling waste dilution are processed.After tested, its treatment effect can be removed COD and reach 37%, and adds iron filings that total amount is equal to process under the same conditions the waste water of same sample ingredient, and removal effect is 26%.
Embodiment 2:
One. the preparation of Fe-based amorphous material
(1) first by the atomic percent of iron 77%, silicon 11%, boron 12%, take raw material;
(2) get the glass tube of one end sealing, its bottom and side have a passage; Load weighted raw material is put into glass tube bottom uniformly, then use rubber stopper with protective gas pipeline glass tube mouth of pipe jam-pack, to carry out gas shield melting and to prevent that gas from overflowing from upper end; Glass tube is placed on the cuvette holder of smelting furnace, makes the just in time induction coil place in smelting furnace of raw material in glass tube, and the protective gas pipeline of rubber stopper is connected on argon gas source;
(3) open protective gas, and regulate air-flow to 0.1 ~ 0.15MPa, make glass tube inside in 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, at 1000 ~ 1200 ℃, make its full and uniform reaction 3 ~ 5 minutes, then stop heating, make its cooling naturally under gas shield state, obtain alloy pig; Behind polishing alloy pig surface, be cut to the sample getting rid of with use;
(5) get rid of band: adopt 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 ℃; Get rid of band carries out under argon shield;
(6) carrying out material processed, is the sheet shaped piece of diameter 1cm by Fe-based amorphous material disintegrating by pulverizer.
Two. the preparation of ferrous metals alloy material
First choose ingot iron, the percentage by weight that accounts for prepared ingot iron with appropriate carbon dust and 0.08%() rare earth magnesium is formulated as the ingot iron of phosphorus content 3%, by lathe, its car become to the spiral bits shape thing of diameter 1cm left and right.
Three. the filling of composite
By iron filings alloy with amorphous metal alloy according to 5:1(weight ratio) ratio mix, notice that, in mixed process, iron filings and amorphous metallic alloy carry out mixed packing, and each layer of metal material is evenly distributed in container.
Four. treatment process
Iron filings and non-crystalline material are loaded according to above-mentioned designation method, and subsequently by waste water injecting reactor, regulating pH value is 3 ~ 5, and adds hydrogen peroxide according to the amount of waste water and hydrogen peroxide 1000:1, by air blast, carries out Air Exposure 2 ~ 3 hours.
Five. treatment effect
By testing in engineering, oil drilling waste in Processing Example 1, adopts method of testing in embodiment 1 according to the method described above, and its treatment effect can be removed COD and reach 48%, and adding iron filings that total amount is equal to process under the same conditions the waste water of same sample ingredient, removal effect is 32%.
Claims (8)
1. a ferrous alloy composite, it is characterized in that, the iron filings that are 90%-65% by percentage by weight and percentage by weight are that 10%～35% Fe-based amorphous alloy chip mixes and forms, the phosphorus content of described iron filings is 1%～3%, in iron filings, also comprise the rare earth magnesium of 0 < percentage by weight≤0.1%, described Fe-based amorphous alloy comprises the following component by atomic percent: 78% iron, 9% silicon and 13% boron; Or 77% iron, 11% silicon and 12% boron.
2. 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.
3. 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.
4. the preparation method of ferrous alloy composite claimed in claim 1, is characterized in that, comprises the following 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, weigh proportioning, refine the alloy of selected components under the protection of inert gas; (b) utilize rapid solidification equipment, the alloy of refining is carried out under the protection of inert gas to remelting, when composition melts when even, utilize instantaneous differential pressure that molten metal splash is processed and obtained amorphous ribbon to carrying out rapid solidification on running roller; (c) utilize disintegrating apparatus amorphous ribbon to be pulverized to the amorphous metal fragment that is less than 1cm for diameter;
(3) iron filings alloy is proportionally mixed and be get final product with amorphous metal alloy;
Wherein, in step (1), in the preparation of ingot iron, also add the rare earth magnesium of 0 < percentage by weight≤0.1%.
5. preparation method as claimed in claim 4, is characterized in that, in step (1), iron filings are to be processed into the spiral bits shape metal fragment that diameter is 0.5-1.5cm.
6. the method for the processing oil drilling waste of the ferrous alloy composite described in claim 1-3 any one, it is characterized in that, comprise the following steps: ferrous alloy composite is filled in container, oil drilling waste is injected in tank body, by air blast, to inflation in tank body, carries out Air Exposure.
7. the method for processing oil drilling waste as claimed in claim 6, is characterized in that, before Air Exposure, the pH value of oil drilling waste is adjusted into 3～6.
8. the method for processing oil drilling waste as claimed in claim 6, is characterized in that, before Air Exposure, according to the amount of hydrogen peroxide ratio wastewater volume 1:1000～1:200, adds hydrogen peroxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210397847.9A CN102909363B (en) | 2012-10-18 | 2012-10-18 | Iron-base alloy compound material, preparation method thereof and method for disposing petroleum drilling wastewater |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210397847.9A CN102909363B (en) | 2012-10-18 | 2012-10-18 | Iron-base alloy compound material, preparation method thereof and method for disposing petroleum drilling wastewater |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102909363A CN102909363A (en) | 2013-02-06 |
| CN102909363B true CN102909363B (en) | 2014-07-23 |
Family
ID=47608075
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210397847.9A Expired - Fee Related CN102909363B (en) | 2012-10-18 | 2012-10-18 | Iron-base alloy compound material, preparation method thereof and method for disposing petroleum drilling wastewater |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102909363B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104211231A (en) * | 2013-06-05 | 2014-12-17 | 中国石油天然气股份有限公司 | Oil field measure waste liquid treatment method |
| CN105314726B (en) * | 2014-07-01 | 2017-12-12 | 中国科学院宁波材料技术与工程研究所 | A kind of processing method of dyeing and printing sewage |
| CN106277223B (en) * | 2015-09-03 | 2019-04-30 | 苏州金渠环保科技有限公司 | Sewage disposal device |
| CN105177351B (en) * | 2015-09-03 | 2017-01-25 | 杭州友创环境工程技术有限公司 | Water treatment core part |
| CN105174380B (en) * | 2015-09-03 | 2017-12-01 | 广东华碧环保股份有限公司 | A kind of sewage disposal device |
| CN106006916B (en) * | 2016-07-18 | 2020-01-07 | 中国科学院金属研究所 | Method for degrading coking wastewater by using iron-based amorphous alloy |
| CN108018504B (en) * | 2017-12-21 | 2020-05-08 | 青岛云路先进材料技术股份有限公司 | Iron-based amorphous alloy and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1994917A (en) * | 2006-12-07 | 2007-07-11 | 西南石油大学 | Process for preparing highly effective Fe/C microelectrolysis water treating agent |
| CN201313845Y (en) * | 2008-10-15 | 2009-09-23 | 罗观平 | Waste water disposal device by utilizing ductile cast iron scraps |
| CN102070236A (en) * | 2009-11-20 | 2011-05-25 | 中国科学院金属研究所 | Ferrum-based amorphous alloy strip for treating printing and dyeing wastewater and preparation method thereof |
| CN102383069A (en) * | 2011-10-19 | 2012-03-21 | 无锡华冶钢铁有限公司 | Iron-based amorphous alloy used for printing and dying wastewater treatment |
-
2012
- 2012-10-18 CN CN201210397847.9A patent/CN102909363B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1994917A (en) * | 2006-12-07 | 2007-07-11 | 西南石油大学 | Process for preparing highly effective Fe/C microelectrolysis water treating agent |
| CN201313845Y (en) * | 2008-10-15 | 2009-09-23 | 罗观平 | Waste water disposal device by utilizing ductile cast iron scraps |
| CN102070236A (en) * | 2009-11-20 | 2011-05-25 | 中国科学院金属研究所 | Ferrum-based amorphous alloy strip for treating printing and dyeing wastewater and preparation method thereof |
| CN102383069A (en) * | 2011-10-19 | 2012-03-21 | 无锡华冶钢铁有限公司 | Iron-based amorphous alloy used for printing and dying wastewater treatment |
Non-Patent Citations (5)
| Title |
|---|
| Bao Lin et al.Application of Fe-based metallic glasses in wastewater treatment.《Materials Science and Engineering B》.2011,第177卷92-95. * |
| 李天鹏等.微电解技术处理工业废水的研究进展及应用.《工业水处理》.2009,第29卷(第10期),9-13. * |
| 杨子立等.改性粉煤灰在废水处理中的应用进展.《工业水处理》.2011,第31卷(第03期),24-26,56. * |
| 林葆.铁基非晶材料在污水处理中的应用.《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》.2012,(第4期),B027-537. |
| 铁基非晶材料在污水处理中的应用;林葆;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20120415(第4期);B027-537 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102909363A (en) | 2013-02-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102909363B (en) | Iron-base alloy compound material, preparation method thereof and method for disposing petroleum drilling wastewater | |
| Gao et al. | Comprehensive utilization of steel slag: A review | |
| CN105238409B (en) | The linkage stabilizer and restorative procedure of restoration of soil polluted by heavy metal | |
| CN103396806A (en) | Agent and method used for remedying heavy metal polluted soil | |
| CN110218832A (en) | Wind-power spherulitic graphite cast iron pours method nodularization and simplifies treatment process | |
| CN104550223A (en) | Treatment method of Ni and Pb contaminated soil remediation | |
| CN105741899A (en) | Solidification treatment additive, solidification formula and solidification process for radioactive boron-containing waste liquor | |
| CN111850193A (en) | Online quenching and tempering device and method for slag discharging and cooling process of molten steel slag | |
| CN105369119B (en) | A kind of ironcasting material and its production technology | |
| CN104479686A (en) | Curing agent and method for heavy metal | |
| CN107099747B (en) | A kind of production technology for controlling acid-resistant pipeline steel Large Inclusions | |
| CN104531158B (en) | A kind of curing agent and its curing method | |
| CN109576588A (en) | Ocean engineering corrosion-resistant stainless steel pole and preparation method thereof | |
| CN102659215B (en) | Preparation method of polarization modified iron-carbon micro-electrolysis material | |
| CN106987759A (en) | A kind of corrosion-resistant screw-thread steel smelting process containing rare earth element | |
| CN107299249A (en) | A kind of unleaded bell metal of old material regeneration and preparation method thereof | |
| CN103602882B (en) | The pouring molten iron of natural aerodynamic cylinder and melting technology thereof | |
| CN105671247A (en) | External refining method for powder injection dephosphorization for silicon-manganese alloy melt | |
| CN212293627U (en) | Online quenching and tempering device for slag tapping cooling process of molten steel slag | |
| CN101543890A (en) | Drainage agent for automatic steel-pouring of ladle in smelting process | |
| CN109385527B (en) | Method for comprehensively recovering nickel-chromium alloy | |
| CN107384423A (en) | It is a kind of to be used to synchronously repair polycyclic aromatic hydrocarbons contaminated and compound formulation of heavy-metal contaminated soil and preparation method thereof | |
| CN1028311C (en) | Melting pollution removing method for polluted metal by uranium | |
| CN109607854A (en) | A kind of high-content heavy metal ion underwater prevention method | |
| CN102560052B (en) | Heat treatment method for steel pieces with high impact strength and application of steel pieces |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20140723 Termination date: 20161018 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |