CN101716591B - Passivating method for reducing bioavailability of cadmium of acidic cadmium polluted soil - Google Patents
Passivating method for reducing bioavailability of cadmium of acidic cadmium polluted soil Download PDFInfo
- Publication number
- CN101716591B CN101716591B CN2009102271350A CN200910227135A CN101716591B CN 101716591 B CN101716591 B CN 101716591B CN 2009102271350 A CN2009102271350 A CN 2009102271350A CN 200910227135 A CN200910227135 A CN 200910227135A CN 101716591 B CN101716591 B CN 101716591B
- Authority
- CN
- China
- Prior art keywords
- cadmium
- soil
- passivator
- acidic
- full dose
- 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
Images
Landscapes
- Processing Of Solid Wastes (AREA)
- Soil Conditioners And Soil-Stabilizing Materials (AREA)
Abstract
The invention discloses a passivating method for reducing bioavailability of cadmium in acidic cadmium polluted soil. The passivant adopted by the method is industrial waste which is obtained by recycling pulp alkaline liquor with hydrated lime in the paper mill. The industrial waste generally contains 0.8g/kg-3.0g/kg of effective silicon, 0.6g/kg-2.0g/kg of effective iron and 100.0mg/kg-400.0mg/kg of effective phosphorus. The passivating method of the invention has the advantages of resource conservation, environmental friend, low cost, simple operation and the like, and can effectively control the soil heavy metal pollution and reduce the bioavailability of cadmium in acidic cadmium polluted soil.
Description
Technical field
The present invention relates to a kind of restorative procedure of heavy-metal contaminated soil, relate in particular to a kind of method that reduces the heavy metal in soil bioavailability of cadmium by chemical means.
Background technology
Paddy soil heavy metal pollution is the severe problem that present China agricultural environment is faced.In recent years, along with industrialization and intensive agriculture expanding economy, China's heavy metals in farmland pollution situation is more and more serious.Ministry of Agriculture's rice and quality of item supervision and inspection center thereof inspected the result by random samples to the security of national market rice in 2002 and show, what heavy metals exceeding standard was the most serious is plumbous, exceeding standard rate is 28.4%, next is cadmium (Cd), exceeding standard rate is that 10.3% (Peng Hua, Ji Xionghui make widely known pearl, Liu Zhaobing: " mild or moderate heavy-metal contaminated soil agricultural safety production technique progress ", " Hunan agricultural sciences " 2008[2]).Early 1990s, China's cadmium pollution cultivated area reaches 1.3 * 10
-4Hm
2, relate to 25 areas of 11 provinces and cities, annual " the cadmium rice " 5.0 * 10 of producing
7Kg (wangkai honor: " China's farmland cadmium pollution present situation and improvement thereof utilize countermeasure ", " agriculture environmental protection ", 1997,16[6]).1998～2000 years, Hunan Province's heavy metal pollution ad hoc survey and agricultural environment quality-monitoring result in recent years show, the contaminated cultivated area in Hunan Province has accounted for 23.7% of the whole province total cultivated area, about 27% farmland irrigating water and about 25% farmland atmosphere have been subjected to pollution in various degree in addition, major pollutants are heavy metal element (ecliptic friends such as cadmium, lead, Chen Huiping, Gong Gaotang: " main type rice soil cadmium pollution improvement in Hunan Province's utilizes research ", " agricultural modernization research ", 2000,21[6]).The cadmium poisoning incident appears in Suichang County, Zhejiang Province and area, Wenzhou in succession, the cause of disease all comes from the cadmium pollution in local farmland, the brown rice cadmium content reaches 1.17mg/kg and 1.30mg/kg (Li Jiqiang respectively, Chen Xiyong, Tang Yijia: " Environmental Cadmium Pollution and to the research of Human Health Effect ", " Chinese public health ", 2001,17[3]).Tianyuan District Ma Jiahe town, zhuzhou, hunan province city people's more than 1800 Singapore and Malaysia village, more than 1100 villager is diagnosed as cadmium and exceeds standard, and wherein the people is identified as severe overweight more than 200.
In order to reduce the absorption accumulation of paddy rice on the heavy-metal contaminated soil, mainly studied dual mode at present both at home and abroad to cadmium: the one, the cadmium in the soil is converted into the indissoluble attitude, promptly the activated state cadmium in the soil is by " passivation ", thereby makes paddy rice be difficult to absorb; The 2nd, cadmium is removed from soil, promptly utilize engineering or biological method " reparation " cadmium pollution soil.To repair required fund bigger because of engineering for the latter, be difficult to carry out large tracts of land and promote, and biological restoration is difficult to reach in a short time safety standard for the mild or moderate level of pollution.Therefore, ensure in China under the fundamental state policy of grain security, at the bigger arable land of mild or moderate cadmium pollution area, take efficiently to reduce the soil bioavailability of cadmium, i.e. activated state cadmium in " passivation " soil (comprising that low kind, agronomic measures and the passivating technique of absorbing combines), be widely regarded as and a kind ofly can have ensured national food safety, can realize the efficient ways of quality of rice safety again.Current acid Cd contaminated soil mainly adopts the lime passivation, and its major defect is that lime alkalescence is strong excessively, and is big to the geobiont availability influence, may cause secondary pollution, and the cost of outsourcing lime is bigger, and passivation effect also has to be strengthened.Therefore, how to improve and optimize " passivation " method of activated state cadmium in the soil, concerning those skilled in the art, then have more realistic meaning.
Summary of the invention
The technical problem to be solved in the present invention is to overcome the deficiencies in the prior art, a kind of resources conservation, environmental friendliness is provided, cost is lower, easy and simple to handle and can effectively administers the passivating method of the reduction bioavailability of cadmium of acidic cadmium polluted soil of heavy metal pollution of soil.
For solving the problems of the technologies described above, the technical scheme that the present invention proposes is a kind of passivating method that reduces bioavailability of cadmium of acidic cadmium polluted soil, it is characterized in that: the passivator that described passivating method adopts is that the paper mill utilizes the trade waste (this trade waste is " white clay " that the paper mill is commonly called as) after white lime reclaims paper pulp alkali lye.
In the above-mentioned passivating method, the basicity of described trade waste (in the CaO that detects) is preferably 2.0g/kg～10.0g/kg.
In the above-mentioned passivating method, preferably contain effective silicon 0.8g/kg～3.0g/kg, effective iron 0.6g/kg～2.0g/kg and available phosphorus 100.0mg/kg～400.0mg/kg in the described trade waste.
In the above-mentioned passivating method, contain preferably in the described trade waste that full dose cadmium 0.2mg/kg is following, the plumbous 30.0mg/kg of full dose following, full dose copper 35.0mg/kg is following, full dose zinc 100mg/kg is following and below the full dose arsenic 10.0mg/kg
In the above-mentioned passivating method, the concrete grammar that utilizes described passivator to carry out passivation is preferably: before described acidic cadmium polluted soil is turned over fertilising, described passivator is evenly spread fertilizer over the fields at soil surface, and then use base manure.Suggestion does not mix with carbon ammonium, urea class nitrogenous fertilizer and uses, otherwise can cause that ammonium changes ammonia into rapidly and evaporate in the atmosphere.
In the above-mentioned passivating method, when cadmium content is 0.3mg/kg～1.0mg/kg in the described acidic cadmium polluted soil when cadmium pollution (slight), the amount of application of described passivator is preferably 1500kg/hm
2～4500kg/hm
2In the above-mentioned passivating method, when cadmium content was 1.0mg/kg～3.0mg/kg in the described acidic cadmium polluted soil, the amount of application of described passivator was preferably 4500kg/hm
2～13500kg/hm
2After using by above-mentioned consumption, better to the accumulative effect that reduces cadmium in the rice grain, the cadmium in the brown rice is controlled at below the national safety standard.
The passivation principle of technique scheme mainly comprise following some:
(1) contains alkaline matters such as calcium carbonate in the described passivator, this makes this passivator have stronger alkalescence, through assay, the basicity of this passivator (CaO) is generally 2.0g/kg～10.0g/kg, but far below the basicity level of lime (40g/kg～60g/kg), therefore using a certain amount of this passivator can significantly improve pH in soil behind acidic cadmium polluted soil, thereby make the active cadmium in the soil under alkali condition, form the slightly solubility precipitation, but pH in soil is sharply raise and cause the variation of animal and microorganism in the soil, can not influence the bio-diversity of soil; Its ion-reaction equation is mainly:
(2) the effective silicon that contains in the described passivator is a kind of strong adsorbability material, can adsorb the cadmium ion in the soil, reduces the mobility of cadmium ion in the soil liquid;
(3) iron ion that contains in the described passivator easily forms Fe (OH) under alkali condition
3Material such as colloid and iron oxide, these materials have stronger adsorption capacity equally to the cadmium ion in the soil, thereby reduce the mobility of cadmium ion in the soil liquid;
(4) the phosphoric acid class material that contains in the described passivator also can generate the slightly solubility precipitation with the ion cadmium reaction in the soil, and its ion-reaction equation is:
(5) contain in the described passivator that full dose Cd 0.20mg/kg is following, full dose Pb 30.0mg/kg following, full dose Cu 35.0mg/kg is following, full dose Zn100mg/kg is following and below the full dose As 10.0mg/kg, all be lower than the natural background value of national soil quality standard, can not constitute secondary pollution soil environment.
Compared with prior art, the invention has the advantages that: at first, adopted a kind of existing trade waste as passivator in the passivating method of the present invention, this passivator is wide material sources not only, cost is low, and can effectively reduce the biological effectiveness of cadmium in the acidic cadmium polluted paddy soil, realized the utilization again of existing trade waste resource simultaneously, turn waste into wealth, solved the environmental pollution hidden danger that this trade waste stacking process neutral and alkali infiltration brings, all significant to economizing on resources, protect environment; Secondly, the passivator that adopts in the passivating method of the present invention can not destroy the acid-base balance of soil, can not cause negative influence to the microenvironment that has soil now, can not form the secondary pollution to soil environment; At last, passivating method of the present invention is simple to operate, reliable, and passivator is used conveniently (spread fertilizer over the fields evenly and get final product), instant effect, and economic benefit is obvious, to the heavy metal pollution of control soil, ensures that grain security is all significant.
Description of drawings:
Fig. 1 adopts passivating method of the present invention to handle the passivation effect figure of back to this season paddy rice brown rice Cd content in the embodiment of the invention 2;
Fig. 2 adopts passivating method of the present invention to handle the after effect figure of back to the rape seed Cd content second season in the embodiment of the invention 2.
The specific embodiment
Below the passivator used among each embodiment be Yueyang paper plant and utilize white powder waste residue after white lime reclaims paper pulp alkali lye, be " white clay " that this area is commonly called as, the basicity of this passivator (in the CaO that detects) is 5.09g/kg, contain effective silicon 1.11g/kg in this passivator, effective iron 1.33g/kg and available phosphorus 231.7mg/kg, full dose cadmium in this passivator is 0.11mg/kg, the plumbous 9.70mg/kg of full dose, full dose copper 13.3mg/kg, full dose Zn 81.0mg/kg, full dose As 4.10mg/kg, each harmful substance is (for example plumbous, copper, zinc, arsenic) content all is lower than the natural background value of national soil quality standard.Below among each embodiment used lime be white lime, its basicity (in the CaO that detects) is 54.7g/kg, the full dose cadmium is 0.47mg/kg.
Embodiment 1 (pot experiment):
Present embodiment adopts the passivation effect of pot experiment research the present invention to two kinds of acid grounds (wattenshlick field and yellow mud field) cadmium activity.Test is provided with three processing: 1. CK, do not execute passivator; 2. using passivator 4g/kg of the present invention (amounts to the field consumption and is about 9000kg/hm
2); 3. (amount to the field consumption is 9000kg/hm to liming 4g/kg
2), to compare the passivation effect of passivator of the present invention.Each handles triplicate, and random packet is arranged, and establishes guard rows.The whiteware basin alms bowl of 27cm * 30cm is used in test, (aperture is 0.3cm * 0.3cm) to soil through air-dry sieving before the dress basin, every basin is adorned native 9.0kg, on every basin, use simultaneously certain nitrogen, phosphorus, potassic fertilizer, the passivator of the present invention that wherein contains mixing in the fertilizer of a basin contains the lime of mixing in the fertilizer of one basin.The measure of duration of test cultivation management is consistent with field management.The chemical property of dress basin soil sees the following form 1.
Supply the chemical property of examination soil among table 1: the embodiment 1
The exchange state cadmium adopts CaCl in the soil
2Lixiviate-atomic absorption spectrophotometry (graphite furnace) is measured, and the cadmium in paddy rice brown rice and the straw is the cadmium content after atomic absorption spectrophotometry (graphite furnace) mensuration is cleared up after adopting nitric acid-perchloric acid mixed acid to clear up.
Result of the test shows, uses passivator of the present invention or lime to cadmium content influence remarkable (influence the results are shown in following table 2) in soil cadmium form and paddy rice brown rice and the straw.Compare with the CK contrast of not executing passivator, use passivator of the present invention or lime and all can significantly reduce exchange state cadmium content in the soil, both effects are approaching substantially.The exchange state cadmium content had reduced by 30.5% than the CK contrast after passivator of the present invention was used in the wattenshlick field, the yellow mud field has reduced by 64.6%, and the alkalescence of passivator of the present invention only is 1/10 of lime, and other silicon, iron, phosphorus in the used passivator of the present invention have been strengthened its comprehensive passivation to exchangeability cadmium in the soil, non-secondary pollution is little to the geobiont availability influence.
Table 2: soil cadmium form influenced result (unit: mg/kg)
The exchange state cadmium is the main form that plant absorbing is utilized in the soil, and its content will obviously influence the absorption accumulation of plant.The result of table 3 shows, uses passivator of the present invention or lime and all can significantly reduce cadmium content in paddy rice brown rice and the straw, and make the brown rice cadmium content reach national food sanitary standard (GB2715-2005), and it is approaching substantially that both reduce the effect of brown rice cadmium content.After passivator of the present invention was used in the wattenshlick field, cadmium content had reduced by 61.0% and 34.3% than the CK contrast respectively in paddy rice brown rice and the straw; After passivator of the present invention was used in the yellow mud field, paddy rice brown rice and straw cadmium content had reduced by 61.5% and 60.5% than the CK contrast respectively.This shows that passivator of the present invention has tangible passivation effect to acidic cadmium polluted soil, use in right amount and can significantly reduce exchange state cadmium content in the soil, reduce crop and absorb accumulation.
Table 3: cadmium content in paddy rice brown rice and the straw influenced result (unit: mg/kg)
Embodiment 2 (field test of in-situ passivation):
Present embodiment employing field plot trial (paddy rice-rape crop rotation) research the inventive method absorbs the influence of accumulation Cd and the after effect that rape seed Cd is accumulated to this season paddy rice brown rice.Test site is carried out in the Xiangtan City Yuetang District village of dripping, and is the moisture soil that river drift forms for examination soil, and its chemical property sees the following form shown in 4.Test is provided with 3 processing: 1. CK, do not use passivator; 2. use passivator 3000kg/hm of the present invention
23. use passivator 6000kg/hm of the present invention
2Rice application first season passivator of the present invention, the second season, rape was not used, and concrete application process is evenly spread fertilizer over the fields passivator at soil surface, and then is used base manure for before this acidic cadmium polluted moisture soil is turned over fertilising.The chemical fertilizer of all processing, the applications of pesticide and irrigation management are all consistent.The cadmium content of paddy rice brown rice and rape seed adopts nitric acid-perchloric acid mixed acid to clear up back atomic absorption spectrophotometry (graphite furnace) and measures.
Supply the chemical property of examination soil among table 4: the embodiment 2
The test effect of present embodiment is as follows:
1, to the paddy rice action effect of (first season)
After utilizing the present embodiment method that the cadmium pollution paddy soil is tested, to the first season paddy rice test effect as shown in Figure 1, as seen from Figure 1, per hectare uses that cadmium content reduces by 38.4% and 58.4% than the CK contrast respectively in the paddy rice brown rice that passivator 3000kg of the present invention, 6000kg handle, wherein per hectare uses that Cd content is 0.194mg/kg in the paddy rice brown rice that passivator 6000kg handles, and reaches national food hygienic standard (GB2715-2005).Therefore, employing the inventive method can significantly reduce the cadmium content in the paddy rice brown rice, and acidic cadmium polluted paddy soil cadmium is had tangible passivation effect.
2, to the rape action effect of (second season)
After utilizing the present embodiment method that the cadmium pollution paddy soil is tested, to the second season rapeseed cultivation result of the test be illustrated in fig. 2 shown below, as seen from Figure 2, Cd content still significantly is lower than contrast in the second season crop oil vegetable seed grain.Wherein, per hectare uses that cadmium content reduces by 16.4% and 31.8% than the CK contrast respectively in the rape seed of passivator 3000kg, 6000kg, adopts the after effect of the inventive method obvious.
Claims (2)
1. passivating method that reduces bioavailability of cadmium of acidic cadmium polluted soil is characterized in that: the passivator that described passivating method adopts is that the paper mill utilizes the trade waste after white lime reclaims paper pulp alkali lye; The basicity of described trade waste is 2.0g/kg～10.0g/kg; Contain effective silicon 0.8g/kg～3.0g/kg, effective iron 0.6g/kg～2.0g/kg and available phosphorus 100.0mg/kg～400.0mg/kg in the described trade waste;
The concrete grammar that utilizes described passivator to carry out passivation is: before described acidic cadmium polluted soil is turned over fertilising, described passivator is evenly spread fertilizer over the fields at soil surface, and then use base manure, and do not mix with carbon ammonium, urea class nitrogenous fertilizer and use; When cadmium content in the acidic cadmium polluted soil was 0.3mg/kg～1.0mg/kg, the amount of application of described passivator was 1500kg/hm
2～4500kg/hm
2When cadmium content in the acidic cadmium polluted soil was 1.0mg/kg～3.0mg/kg, the amount of application of described passivator was 4500kg/hm
2～13500kg/hm
2
2. passivating method according to claim 1 is characterized in that: contain in the described trade waste that full dose cadmium 0.2mg/kg is following, the plumbous 30.0mg/kg of full dose following, full dose copper 35.0mg/kg is following, full dose zinc 100mg/kg is following and below the full dose arsenic 10.0mg/kg.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009102271350A CN101716591B (en) | 2009-12-08 | 2009-12-08 | Passivating method for reducing bioavailability of cadmium of acidic cadmium polluted soil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009102271350A CN101716591B (en) | 2009-12-08 | 2009-12-08 | Passivating method for reducing bioavailability of cadmium of acidic cadmium polluted soil |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101716591A CN101716591A (en) | 2010-06-02 |
| CN101716591B true CN101716591B (en) | 2011-05-11 |
Family
ID=42431282
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009102271350A Expired - Fee Related CN101716591B (en) | 2009-12-08 | 2009-12-08 | Passivating method for reducing bioavailability of cadmium of acidic cadmium polluted soil |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101716591B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103286118B (en) * | 2013-05-17 | 2015-04-22 | 中国科学院华南植物园 | Method for reducing cadmium content in grasses and vegetables |
| CN103275725B (en) * | 2013-06-07 | 2015-01-21 | 中南大学 | Chemical fixing agent for heavy metal contaminated soil remediation and preparation and application thereof |
| CN104492797B (en) * | 2014-12-09 | 2016-08-24 | 江苏盖亚环境工程有限公司 | A kind of restorative procedure of heavy metal pollution acid ground |
| CN109454101B (en) * | 2018-09-30 | 2020-10-13 | 中国科学院南京土壤研究所 | Method for removing soil cadmium by using ferric trichloride and phosphate |
| CN111213556A (en) * | 2020-02-10 | 2020-06-02 | 中南林业科技大学 | Safe production method of rice for medium and light cadmium-polluted soil |
-
2009
- 2009-12-08 CN CN2009102271350A patent/CN101716591B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN101716591A (en) | 2010-06-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102093896B (en) | Soil conditioner for reducing bioavailability of cadmium in acid heavy cadmium polluted soil and method for improving soil | |
| CN103004439B (en) | Combined prevention and control method for cadmium exceeding of rice in medium-light cadmium-polluted soil | |
| CN105802637B (en) | A kind of soil heavy metal passivant and preparation method and the passivating method to Cadmium in Soil | |
| CN107318548B (en) | Method for safely producing rice in cadmium-polluted soil | |
| CN101928179B (en) | Slow release fertilizer having soil remediation function and soil contamination remediation method | |
| CN103951530B (en) | A kind of peptide calcium salt in-situ passivation agent of administering heavy-metal contaminated soil and preparation method thereof and application | |
| CN108165276A (en) | A kind of composite conditioner suitable for northern alkaline soil heavy metal pollution | |
| CN107350281A (en) | One kind is applied to northern farmland soil of sewage irrigation area passivator and its application process | |
| CN101716591B (en) | Passivating method for reducing bioavailability of cadmium of acidic cadmium polluted soil | |
| CN104194798B (en) | Organic modifier capable of passivating copper, zinc, arsenic and chromium in vegetable field soil | |
| CN101722182A (en) | Method for rapid in-situ remediation soil polluted by heavy metals | |
| CN111213556A (en) | Safe production method of rice for medium and light cadmium-polluted soil | |
| CN107880888A (en) | A kind of Cadmium in Soil passivator and processing method | |
| CN106034454B (en) | Improve paddy growth in arsenic pollution rice field and reduces the water-fertilizer conditioning method that arsenic absorbs | |
| Sharma et al. | Sustainable management of sodic soils for crop production: opportunities and challenges | |
| CN107384433A (en) | A kind of soil heavy metal passivant | |
| CN104946262A (en) | Acidic farmland soil heavy metal cadmium pollution in situ passivation conditioner and preparation method thereof | |
| CN103058717B (en) | Heavy metal treatment technology for heavy metal adsorption, dehydration and fertilizer preparation | |
| JP2013174557A (en) | Radioactive material decontamination agent and radioactive material decontamination method using microorganism and humus | |
| CN103820124A (en) | Soil conditioner and application method thereof | |
| CN108821843A (en) | Conditioner and its preparation and application for the Farmland contamination reparation of mining area periphery | |
| Islam et al. | A critical review of soil phosphorus dynamics and biogeochemical processes for unlocking soil phosphorus reserves | |
| CN106866305A (en) | A kind of ecological activation conditioner of heavy-metal contaminated soil and preparation method thereof | |
| CN104855029A (en) | Simple formula fertilization method for plant prevention and treatment of heavy metal pollution | |
| CN109913233A (en) | A kind of water paddy soil heavy metal passivation modifying agent |
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 | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Assignee: Hunan Longke industry limited company Assignor: Hunan Soil and Fertilizer Inst. Contract record no.: 2011430000265 Denomination of invention: Passivating method for reducing bioavailability of cadmium of acidic cadmium polluted soil Granted publication date: 20110511 License type: Exclusive License Open date: 20100602 Record date: 20111027 |
|
| ASS | Succession or assignment of patent right |
Owner name: HUNAN YUFENG AGRICULTURAL ECOLOGICAL ENGINEERING C Free format text: FORMER OWNER: HUNAN SOIL AND FERTILIZER INST. Effective date: 20150330 |
|
| COR | Change of bibliographic data |
Free format text: CORRECT: ADDRESS; FROM: 410125 CHANGSHA, HUNAN PROVINCE TO: 412000 ZHUZHOU, HUNAN PROVINCE |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20150330 Address after: 412000 No. nine Changjiang South Road, Tianyuan District, Hunan, Zhuzhou Patentee after: Hunan Yufeng Agricultural Ecological Engineering Co., Ltd. Address before: 410125 Furong district, Hunan, Changsha province Yuanda two road Patentee before: Hunan Soil and Fertilizer Inst. |
|
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20110511 Termination date: 20201208 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |