CN106947493B - Green improving synergist for acid soil and preparation method thereof - Google Patents

Green improving synergist for acid soil and preparation method thereof Download PDF

Info

Publication number
CN106947493B
CN106947493B CN201710187572.9A CN201710187572A CN106947493B CN 106947493 B CN106947493 B CN 106947493B CN 201710187572 A CN201710187572 A CN 201710187572A CN 106947493 B CN106947493 B CN 106947493B
Authority
CN
China
Prior art keywords
soil
potassium
raw materials
synergist
acid
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
Application number
CN201710187572.9A
Other languages
Chinese (zh)
Other versions
CN106947493A (en
Inventor
司贤宗
张翔
索炎炎
余琼
毛家伟
李亮
王亚宁
李国平
余辉
刘成用
王福安
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henan Yuzhongao Agricultural Science & Technology Co ltd
Institute of Plant Nutrition and Resource Environmentof of Henan Academy of Agricultural Sciences
Original Assignee
Henan Yuzhongao Agricultural Science & Technology Co ltd
Institute of Plant Nutrition and Resource Environmentof of Henan Academy of Agricultural Sciences
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henan Yuzhongao Agricultural Science & Technology Co ltd, Institute of Plant Nutrition and Resource Environmentof of Henan Academy of Agricultural Sciences filed Critical Henan Yuzhongao Agricultural Science & Technology Co ltd
Priority to CN201710187572.9A priority Critical patent/CN106947493B/en
Publication of CN106947493A publication Critical patent/CN106947493A/en
Application granted granted Critical
Publication of CN106947493B publication Critical patent/CN106947493B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K17/00Soil-conditioning materials or soil-stabilising materials
    • C09K17/40Soil-conditioning materials or soil-stabilising materials containing mixtures of inorganic and organic compounds
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2101/00Agricultural use
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2109/00MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE pH regulation

Abstract

The invention belongs to the technical field of soil improvement, and particularly discloses a green improving synergist for acid soil and a preparation method thereof. The material consists of the following raw materials in percentage by weight: 30-50% of calcium oxide, 20-30% of magnesium oxide, 1-5% of polyepoxysuccinic acid or polyepoxysuccinic acid potassium and 15-49% of filler. Before the polyepoxysuccinic acid (potassium) is used as a scale inhibitor in water treatment, the polyepoxysuccinic acid (potassium) is used as a raw material of a soil conditioner for the first time; the raw materials of calcium oxide, magnesium oxide, polyepoxysuccinic acid (potassium) and filler adopted in the invention are nontoxic and harmless to crops, soil and human health, so the soil improvement synergist formed by combining the raw materials is a green product; by applying the soil conditioner, the pH value of plough layer soil of 0-20cm, the number of bacteria and actinomycetes can be obviously increased, the volume weight of plough layer soil of 0-20cm is reduced, and the agronomic characters and the yield of peanuts are improved.

Description

Green improving synergist for acid soil and preparation method thereof
Technical Field
The invention belongs to the technical field of soil improvement, and particularly relates to a green improving synergist for acid soil and a preparation method thereof.
Background
The normal growth and development of plants depend on a good soil environment. However, in nature, the soil in which plants grow often has various obstacle factors that limit the growth of plants. For example, large areas of saline-alkali soil on the land surface of the world have high salinity; high concentration of H in acid soil+,Al3+,Mn2+And Fe2+Etc.; the flooded soil contains excessive reducing substances and Fe2+Etc.; calcareous soil lacks sufficient available phosphorus, iron, zinc, and the like. With the continuous application of chemical fertilizer and the continuous release of H from the root system of high-yield crops to soil+The pH value of the soil is in a descending trend year by year, and the field blocks with the pH value of the plough layer soil lower than 5.5 are increased year by year, so that the crop yield is low, the fertilizer application is ineffective, and the plant diseases and insect pests are serious, so that the serious acidification of the soil becomes a limiting factor for the development of agricultural production.
Soil conditioners (Soil conditioners) are mainly used for improving Soil properties so as to be beneficial to crop growth, but not used as substances for providing nutrients required for crop growth, have the main functions of improving physical, chemical and biological properties of Soil, and have obvious effects of maintaining Soil water content, improving Soil granular structure, adjusting Soil pH, reducing Soil saline-alkali hazards, repairing polluted Soil and the like. In recent years, the variety of soil conditioners has been more and more developed, and korea canula divides the soil conditioners into 4 types, i.e., organic types, mineral types, polymer types, and other types. The existing soil conditioner is applied all year round, so that the field soil has resistance to the soil conditioner, and the original soil improvement effect cannot be achieved. Therefore, it is necessary to develop a novel soil conditioner.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a green improving synergist for acid soil and a preparation method thereof.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the green improving synergist for the acid soil comprises the following raw materials in percentage by weight:
30-50% of calcium oxide, 20-30% of magnesium oxide, 1-5% of polyepoxysuccinic acid or polyepoxysuccinic acid potassium and 15-49% of filler.
Preferably, the quality indexes of the polyepoxysuccinic acid are as follows: the content of active substances is more than or equal to 95wt%, the pH value of 10 mass times of water diluent is 7.5-11.0, and the degradation rate is more than or equal to 60%; the quality indexes of the polyepoxy potassium succinate are as follows: k2The content of O is 5-25 wt%, the content of effective substances is more than or equal to 95wt%, the pH value of 10 mass times of water diluent is 7.5-11.0, and the degradation rate is more than or equal to 60%.
Preferably, the filler is bentonite.
The invention provides two preparation methods, which specifically comprise the following steps:
the preparation method comprises the following steps: weighing raw materials according to a proportion, mixing, crushing and screening until the particle size of the materials is less than or equal to 1mm, and obtaining a finished product; and finally, metering and packaging the finished product to obtain the product.
The preparation method 2 comprises the following steps: weighing raw materials according to a certain proportion, mixing, and then sequentially crushing, granulating, drying and packaging to obtain the product. Further, after drying, cooling and screening the mixture until the particle size of the material particles is less than or equal to 4.5mm and less than or equal to 2.5mm, and obtaining a finished product; and finally, metering and packaging the finished product to obtain the product.
Calcium oxide (calcium oxide), an inorganic compound, has the chemical formula CaO, commonly known as quicklime. The physical property is white powder on the surface, the powder has hygroscopicity, quicklime reacts with water to generate calcium hydroxide, and the reaction equation is as follows: CaO + H2O =Ca(OH)2The calcium hydroxide is a binary medium-strong alkali, and the agricultural Bordeaux mixture with bactericidal action prepared from calcium hydroxide and copper sulfate solution can be used as agricultural chemical, or the proper quantity of cookedLime is added into soil to neutralize acidity, improve acid soil and crop living environment, and release Ca to soil2+For the absorption and utilization of plants. Magnesium oxide (chemical formula: MgO) is an oxide of magnesium, and is a white powder at room temperature, MgO + H2O→Mg(OH)2Has weak hygroscopicity, can improve the pH value of soil after being applied into the soil, and simultaneously releases Mg to the soil2+For the absorption and utilization of plants. The polyepoxysuccinic potassium is potassium salt of polyepoxysuccinic acid, and is alkaline; polyepoxysuccinic acid (PESA) is a nitrogen-free and non-phosphorus organic compound, and the active group of the polyepoxysuccinic acid has strong chelating capacity on cations such as metal in water, and is a green water treatment chemical; the exchange effect of the polyepoxysuccinic potassium in potassium ions in soil can chelate Al3+,Mn2+And Fe2+The cations can also increase the effectiveness of medium and trace nutrient elements necessary for plants and promote the growth and development of the plants.
Has the advantages that:
1. before the polyepoxysuccinic acid (potassium) is used as a scale inhibitor in water treatment, the polyepoxysuccinic acid (potassium) is used as a raw material of a soil conditioner for the first time;
2. the raw materials of calcium oxide, magnesium oxide, polyepoxysuccinic acid (potassium) and filler adopted in the invention are nontoxic and harmless to crops, soil and human health, so the soil improvement synergist formed by combining the raw materials is a green product;
3. by applying the soil conditioner, the pH value of plough layer soil of 0-20cm, the number of bacteria and actinomycetes can be obviously increased, the volume weight of plough layer soil of 0-20cm is reduced, and the agronomic characters and the yield of peanuts are improved.
Drawings
FIG. 1: the invention relates to one of the production processes of an acid soil green improvement synergist.
FIG. 2: the second production process of the green improving synergist for acid soil of the invention.
FIG. 3: influence of different treatments on soil volume weight (g/cm) of plough layer of 0-20cm in peanut harvesting period3)。
Detailed Description
The present invention will be described in further detail with reference to specific examples.
The quality indexes of the polyepoxy succinic acid potassium in the following examples are: k2The content of O: 5wt%, 10-fold by mass of the pH of a water dilution: 8.5, the content of effective substances is 95wt%, and the degradation rate is 60%.
Example 1
The green improving synergist for the acid soil comprises the following raw materials in percentage by weight: 30% of calcium oxide, 20% of magnesium oxide, 1% of polyepoxy succinic potassium and 49% of bentonite.
The preparation method is shown in a flow chart in figure 1: weighing raw materials according to a proportion, mixing, crushing and screening until the particle size of the materials is less than or equal to 1mm, and obtaining a finished product; and finally, metering and packaging the finished product to obtain the product.
Example 2
The green improving synergist for the acid soil comprises the following raw materials in percentage by weight: 45% of calcium oxide, 25% of magnesium oxide, 3% of polyepoxy succinic potassium and 27% of bentonite.
The preparation method is shown in a flow chart in figure 2: weighing raw materials according to a certain proportion, mixing, and then sequentially crushing, granulating, drying and packaging to obtain the product.
Example 3
The green improving synergist for the acid soil comprises the following raw materials in percentage by weight: 50% of calcium oxide, 30% of magnesium oxide, 5% of polyepoxy succinic potassium and 15% of bentonite.
The preparation method is shown in a flow chart in figure 2: weighing raw materials according to a proportion, mixing, then sequentially crushing, granulating, drying, cooling and screening until the particle size of the material particles is less than or equal to 4.5mm and less than or equal to 2.5mm, and obtaining a finished product; and finally, metering and packaging the finished product to obtain the product.
Application example
1. Materials and methods
1.1 test site and peanut variety tested
The test is arranged in a peanut test field in the village greater than county of blue, village in Zhengyang county of Henan province from 6 months to 10 months in 2016. The soil of the test field is sand ginger black soil, the texture is sticky, the terrain is flat, and the soil fertilityUniform and good drainage and irrigation conditions. 0-20cm plough layer soil foundation soil fertility: 13.3g/kg of organic matter, 0.8g/kg of total nitrogen, 72.6mg/kg of quick-acting nitrogen, 13.8mg/kg of quick-acting phosphorus, 98.3mg/kg of quick-acting potassium, 1.31mg/kg of effective zinc, 5.10 of PH value and 1.42g/cm of soil volume weight of 0-20cm plough layer3
The peanut variety to be tested is resident flower No. 1.
1.2 design of the experiment
The experiment was set up with 4 treatments, T1, controls; t2, soil conditioner A (product of example 1), applied at 600 kg/hm2(ii) a T3, soil conditioner B (product of example 2), applied at 600 kg/hm2(ii) a T4, soil conditioner C (product of example 3), applied at 600 kg/hm2
The application amount of the nitrogen, the phosphorus and the potassium is respectively N120 kg/hm2,P2O590 kg/hm2、K2O 120 kg/hm2The fertilizer varieties comprise urea, calcium superphosphate and potassium chloride, the fertilizer is completely used as a base fertilizer, and peanuts are planted after the fertilizer is spread and ridged. The area of the test cell is 15m2Repeat 3 times, arrange randomly. The planting mode is ridging planting, and the planting density is 18 ten thousand holes/hm2And 2 seeds are sowed in each hole. Other field management is carried out according to the common high-yield field.
1.3 field survey and measurement and sample Collection
1.3.1 soil sample Collection and determination
1kg of a sample of foundation soil (0-20 cm) is collected before land preparation and fertilization, and the foundation soil fertility is measured.
Taking 0-20cm plough layer soil for each treatment in the seedling stage, the flowering stage, the pod bearing stage, the full fruit stage and after harvesting of peanuts according to the soil-water ratio of 1: 10, and measuring the pH value of the soil solution.
In the peanut coning period, 0-20cm of plough layer soil is taken for each treatment, and the soil microorganisms are measured by adopting a flat plate counting method.
And in the peanut harvesting period, measuring the volume weight of 0-20cm plough layer soil by adopting a cutting ring method in each treatment.
1.3.2 harvesting and yield-metering
When the peanuts are harvested, 4m is taken for each treatment2Harvesting, airing, weighing and yield measuring.
1.3.3 other items
And recording the peanut sowing period, the emergence time, the flowering beginning time and the harvesting time.
2 results and analysis
2.1 Effect of different treatments on the pH value of plough layer soil of different growth periods of peanuts
As can be seen from the table 1, the PH values of the plough layer soil with the thickness of 0-20cm in different treatments tend to increase with the growth period of the peanuts; in different growth periods of peanuts, the pH values of 0-20cm plough layer soil are all T4 & gtT 3 & gtT 2 & gtT 1 in sequence, and the pH values of 0-20cm plough layer soil are shown to be increased along with the increase of the contents of calcium oxide, magnesium oxide and polyepoxy succinic potassium in the soil conditioner.
Figure 603604DEST_PATH_IMAGE001
2.2 Effect of different treatments on soil microorganisms in plough layer of 0-20cm in peanut flowering period
As can be seen from Table 2, the abundance of soil biodiversity can be measured by the amount of bacteria and actinomycetes in the soil, and the amount is an important index of soil fertility. The number of bacteria and actinomycetes in the plough layer soil of 0-20cm treated by T2, T3 and T4 is obviously higher than that of the plough layer soil of T1 without applying a soil conditioner, and the application of the soil conditioner can increase the number of bacteria and actinomycetes in the plough layer soil of 0-20 cm; the number of fungi in the soil treated by T2, T3 and T4 is significantly lower than that of T1, which indicates that the application of the soil conditioner can significantly reduce the number of fungi in the soil, and the increase of the number of fungi in the soil is an indicator of soil deterioration, so that the application of the soil conditioner can improve the fertility of the soil. With the increase of the content of calcium oxide, magnesium oxide and polyepoxy succinic potassium in the soil conditioner, the number of fungi in the plough layer of 0-20cm is in a decreasing trend, the number of bacteria and actinomycetes is in a parabolic change trend, and the number of bacteria and actinomycetes in the plough layer of 0-20cm treated by T3 is the highest, which indicates that the content of calcium oxide, magnesium oxide and polyepoxy succinic potassium in the soil conditioner is too high to be beneficial to the proliferation of the bacteria and actinomycetes.
Figure 417976DEST_PATH_IMAGE002
2.3 Effect of different treatments on the soil volume weight of 0-20cm plough layer in the peanut harvesting period
As can be seen from FIG. 3, the volume weights of 0-20cm plough layer soil treated by T1, T2, T3 and T4 in the peanut harvesting period are 1.46 g/cm3、1.40 g/cm3、1.34 g/cm3、1.31 g/cm3The unit weight of the plough layer soil of 0-20cm treated by the T2, the T3 and the T4 is obviously lower than that of the plough layer soil without the application of the soil conditioner T1, which shows that the unit weight of the plough layer soil of 0-20cm can be obviously reduced by applying the soil conditioner; the soil volume weight of 0-20cm plough layer is reduced along with the increase of the content of calcium oxide, magnesium oxide and polyepoxy succinic potassium in the soil conditioner.
2.4 Effect of different treatments on agronomic traits and yield of peanuts
As can be seen from table 3, the stem height, the side branch length, the branch number and the yield of the T2, T3 and T4 treatments were all higher or more than those of T1, indicating that the application of the soil conditioner can significantly increase the stem height, the side branch length, the branch number and the yield of the peanuts; with the increase of the content of calcium oxide, magnesium oxide and potassium polyepoxysuccinate in the soil conditioner, the main stem height, the lateral branch length, the branch number and the yield are increased, wherein the yield of T4 is the highest and is 5166.8 kg/hm2The yield is increased by 25.9%, 8.1% and 1.3% compared with the yield of T1, T2 and T3 respectively.
Figure 552023DEST_PATH_IMAGE003
3 small knot
The soil conditioner can obviously increase the pH value of plough layer soil of 0-20cm, the number of bacteria and actinomycetes, reduce the volume weight of plough layer soil of 0-20cm, and improve the agronomic characters and yield of peanuts at N, P2O5、K2The application amount of O is 120 kg/hm respectively2、90 kg/hm2、120 kg/hm2Applying 600 kg/hm of soil conditioner2Wherein the yield is the highest when 50 percent of calcium oxide, 30 percent of magnesium oxide, 5 percent of polyepoxy succinic potassium and 15 percent of filler are adopted, and is 5166.8 kg/hm2And administration ofSoil conditioner 600 kg/hm2Wherein the yield is almost the same when the calcium oxide is 45 percent, the magnesium oxide is 25 percent, the polyepoxy succinic acid is 3 percent and the filler is 27 percent, and the yield is 5100.1 kg/hm2

Claims (4)

1. The green improving synergist for the acid soil is characterized by comprising the following raw materials in percentage by weight: 30-50% of calcium oxide, 20-30% of magnesium oxide, 1-5% of polyepoxy potassium succinate and 15-49% of bentonite;
the quality indexes of the polyepoxy potassium succinate are as follows: k2The content of O is 5-25 wt%, and the content of effective substances is more than or equal to
95wt%, and 10 times by mass of the water dilution has a pH of 7.5-11.0 and a degradation rate of not less than 60%.
2. A method for preparing the acid soil green improvement synergist according to claim 1, characterized in that: weighing raw materials according to a proportion, mixing, crushing and screening until the particle size of the materials is less than or equal to 1mm, and obtaining a finished product; and finally, metering and packaging the finished product to obtain the product.
3. A method for preparing the acid soil green improvement synergist according to claim 1, characterized in that: weighing raw materials according to a certain proportion, mixing, and then sequentially crushing, granulating, drying and packaging to obtain the product.
4. The method of claim 3, wherein: after drying, cooling and screening the mixture until the particle size of the material particles is less than or equal to 4.5mm and less than or equal to 2.5mm to obtain a finished product; and finally, metering and packaging the finished product to obtain the product.
CN201710187572.9A 2017-03-27 2017-03-27 Green improving synergist for acid soil and preparation method thereof Expired - Fee Related CN106947493B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710187572.9A CN106947493B (en) 2017-03-27 2017-03-27 Green improving synergist for acid soil and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710187572.9A CN106947493B (en) 2017-03-27 2017-03-27 Green improving synergist for acid soil and preparation method thereof

Publications (2)

Publication Number Publication Date
CN106947493A CN106947493A (en) 2017-07-14
CN106947493B true CN106947493B (en) 2020-06-30

Family

ID=59473120

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710187572.9A Expired - Fee Related CN106947493B (en) 2017-03-27 2017-03-27 Green improving synergist for acid soil and preparation method thereof

Country Status (1)

Country Link
CN (1) CN106947493B (en)

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105219397A (en) * 2015-09-21 2016-01-06 山东农业大学 A kind of saline-alkali land soil conditioner and preparation method thereof
CN105622255A (en) * 2015-12-23 2016-06-01 成都新柯力化工科技有限公司 Synergist for fertilizer special for wheat and preparation method for synergist

Also Published As

Publication number Publication date
CN106947493A (en) 2017-07-14

Similar Documents

Publication Publication Date Title
CN102992907B (en) Synergistic loss-control agent of nitrogenous fertilizers and production method thereof
CN106977278A (en) Potassium polyphosphate sugarcane slow-release fertilizer and its production method
CN106278705A (en) A kind of alkaline land improving fertilizer special for organic and its preparation method and application
CN104557222A (en) Soil testing and formulated fertilizer specially used for peanut and preparation method thereof
Bana et al. Moisture-stress management under limited and assured irrigation regimes in wheat (Triticum aestivum): Effects on crop productivity, water use efficiency, grain quality, nutrient acquisition and soil fertility
CN102643651A (en) Material for reclamation of saline-alkali soil and application thereof
CA3149921A1 (en) An additive for soil conditioning and an agricultural composition containing said additive for plant growth
Liu et al. Integrated application of inorganic fertilizer with fulvic acid for improving soil nutrient supply and nutrient use efficiency of winter wheat in a salt-affected soil
CN110981627A (en) Acid soil conditioner
CN103664413A (en) Abamectin active silicon calcium fertilizer and preparation method thereof
CN105367345A (en) Solanaceous greenhouse vegetable special-purpose nutritional compound fertilizer used for improving soil hardening, and application method thereof
CN1944576B (en) Saline-alkali soil amemdment, its preparing method and use
Aechra et al. Effect of soil salinity, phosphorus and biofertilizers on physical properties of soil, yield attributes and yield of cowpea [Vigna unguiculata (L.) Wilczek]
CN109438121A (en) A kind of multifunction soil conditioning-type protecting field speciality fertilizers on commercial crops and the preparation method and application thereof
CN108341717A (en) A kind of promoting root growth diseases prevention tobacco special nutritional conditioner and preparation method thereof
Zubir et al. Growth performance of pineapple (Ananas comosus var. MD2) with different application of granular fertilizer on tropical peat soil
CN106566560B (en) The soil conditioner and preparation method thereof of Xinjiang salt affected soil
CN106947493B (en) Green improving synergist for acid soil and preparation method thereof
CN106748162B (en) Novel special liquid fertilizer for pepper for comprehensive pest control and preparation method thereof
CN107827658A (en) A kind of red soil conditioner of Heisui River gadfly sand compounding chelating boron
Samake Use of locally available amendments to improve acid soil properties and maize yield in the savanna zone of Mali
Van Haute Evaluation of the effects of compost on soil properties, performance and yield of maize and beans in Kenya
CN108770635B (en) Matrix modifier suitable for planting tropical coral island trees
CN107652979A (en) A kind of garden waste biomass carbon soil conditioner and preparation method thereof
CN111592404B (en) Soil remediation type multifunctional biofertilizer and preparation method thereof

Legal Events

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

Granted publication date: 20200630

CF01 Termination of patent right due to non-payment of annual fee