CN105085095B - A kind of preparation, application method and the material of soluble chemical fertilizer slow release device - Google Patents

A kind of preparation, application method and the material of soluble chemical fertilizer slow release device Download PDF

Info

Publication number
CN105085095B
CN105085095B CN201510636316.4A CN201510636316A CN105085095B CN 105085095 B CN105085095 B CN 105085095B CN 201510636316 A CN201510636316 A CN 201510636316A CN 105085095 B CN105085095 B CN 105085095B
Authority
CN
China
Prior art keywords
release device
slow release
soluble chemical
chemical fertilizer
fertilizer slow
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
CN201510636316.4A
Other languages
Chinese (zh)
Other versions
CN105085095A (en
Inventor
吴正景
王柏
米银法
张菊萍
陈迪新
刘保国
彭涛
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 University of Science and Technology
Original Assignee
Henan University of Science and Technology
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 University of Science and Technology filed Critical Henan University of Science and Technology
Priority to CN201510636316.4A priority Critical patent/CN105085095B/en
Publication of CN105085095A publication Critical patent/CN105085095A/en
Application granted granted Critical
Publication of CN105085095B publication Critical patent/CN105085095B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Landscapes

  • Fertilizers (AREA)

Abstract

The present invention relates to a kind of preparation, application method and the material of soluble chemical fertilizer slow release device;The material for preparing soluble chemical fertilizer slow release device is by cement, and perlite is cement foamed, water and anti-crack fiber composition;Preparation method is, by water intaking and cement blowing agent be placed in container, puddle stirring, after thering are a large amount of foams to occur, add cement and perlite, stirring, add anti-crack fiber, stirring, be as used for the material for preparing soluble chemical fertilizer slow release device.Draw materials to be placed in mould and hollow cylinder and two solid cylinders is made;Rubber is wrapped up on solid cylinder surface;Using the solid cylinder of parcel rubber by hollow cylinder sealing two ends, that is, prepare soluble chemical fertilizer slow release device.Load fertilizer during the soluble chemical fertilizer slow release device use, buy in soil.The device can make fertilizer, and from porous bottle wall dissolution part, can be good at same plant growth needs to be synchronised, and can reuse.

Description

A kind of preparation, application method and the material of soluble chemical fertilizer slow release device
Technical field
The present invention relates to a kind of fertilizer slow release device, specifically the preparation of soluble chemical fertilizer slow release device, make With method and material.
Background technology
Depot fertilizer is decomposition, the release for making fertilizer by modes such as coating, parcel, addition inhibitor mostly in the market Time lengthening, is advantageous to improve the utilization rate of fertilizer nutrient, extends the fertilizer term of validity so as to reach.Common depot fertilizer substantially divides For:Sulphur is coated(Fertilizer bag fertilizer), resin coating, urease inhibitorses etc., by the difference of production technology, can be divided into again:Chemical combination type, mixing Type and mix type etc..But the problems such as high production cost, coating agent residual, non-degradable be present.
The content of the invention
The present invention seeks to the deficiency for solution above-mentioned technical problem, there is provided the system of soluble chemical fertilizer slow release device Standby, application method and material.
The present invention is that technical scheme is used by solving above-mentioned technical problem:
A kind of material for being used to prepare soluble chemical fertilizer slow release device, it is characterised in that:Its raw material is by following weight The material composition of part:100 parts of cement, perlite 10-20 parts, cement blowing agent 3-7 parts, water 50-70 parts and anti-crack fiber 1-3 Part.
The preparation method for being used to prepare the material of soluble chemical fertilizer slow release device, comprises the following steps:
Step 1: cement, perlite, cement blowing agent, water and anti-crack fiber are taken according to parts by weight, it is standby;
Step 2: by water intaking and cement blowing agent be placed in container, puddle uniformly, after thering are a large amount of foams to occur, add Cement and perlite, after being again stirring for 15-20min, anti-crack fiber is added, is stirred 5-10 minutes, resulting mixture I, is For preparing the material of soluble chemical fertilizer slow release device.
The method that the material prepares soluble chemical fertilizer slow release device, comprises the following steps:
Hollow cylinder is made Step 1: taking and being placed in the material for preparing soluble chemical fertilizer slow release device in mould Body, it is standby;Take to be placed in mould in the material for preparing soluble chemical fertilizer slow release device again and two solid cylinders be made, It is standby;Prepared solid cylinder diameter is identical with the interior diameter of hollow cylinder, and length is the 1/ of hollow cylinder body length 10-1/4;
Step 2: wrapping up rubber on prepared solid cylinder surface, obtain wrapping up the solid cylinder of rubber;Using The solid cylinder of rubber is wrapped up by hollow cylinder sealing two ends, that is, prepares soluble chemical fertilizer slow release device.
The application method of the soluble chemical fertilizer slow release device, comprises the following steps:
Step 1: according to Plants types choice dissolved fertilizer, according to required selection fertilizer slow release device size;Remove solvable Property chemical fertilizer delayed release device wherein one end parcel rubber solid cylinder, dissolved fertilizer is loaded into hollow cylinder, sealed Mouthful;
It is Step 2: the fertilizer slow release device equipped with dissolved fertilizer is vertical or lie low and be buried in the earth;Vertical embedment flowerpot Depth for soluble chemical fertilizer slow release device upper end under native table 1-2cm, lie low embedment flowerpot depth be native table under 1- 2cm;
Step 3: after 6-12 months, soluble chemical fertilizer slow release device is taken out, supplements fertilizer, can be according to the method described above Recycling.
Beneficial effect is:
Soluble chemical fertilizer slow release device material matching is reasonable, and each composition is mutually coordinated to be reached for preparing by the present invention Prevent water from disposably all dissolving fertilizer, and the purpose that fertilizer can be released slowly into soil;The soluble chemical fertilizer The bar-shaped bottle that delayed release device is formed using a kind of solid cylinder contains suitable a variety of soluble chemical fertilizer, when watering every time, fertilizer For material from porous bottle wall dissolution part, season of growth irrigation times are frequent, the increase of fertilizer stripping quantity, can be good at same plant life Length needs phase coordinate synchronization.The device can reuse.It is economic and environment-friendly using inert materials such as cement.
Brief description of the drawings
Fig. 1 is the structural representation of the hollow cylinder of soluble chemical fertilizer slow release device of the present invention;
Fig. 2 is the section amplification figure of soluble chemical fertilizer slow release device of the present invention.
Embodiment
A kind of material for being used to prepare soluble chemical fertilizer slow release device, it is characterised in that:Its raw material is by following weight The material composition of part:100 parts of cement, perlite 10-20 parts, cement blowing agent 3-7 parts, water 50-70 parts and anti-crack fiber 1-3 Part.
The preparation method for being used to prepare the material of soluble chemical fertilizer slow release device, comprises the following steps:
Step 1: cement, perlite, cement blowing agent, water and anti-crack fiber are taken according to parts by weight, it is standby;
Step 2: by water intaking and cement blowing agent be placed in container, puddle uniformly, after thering are a large amount of foams to occur, add Cement and perlite, after being again stirring for 15-20min, anti-crack fiber is added, is stirred 5-10 minutes, resulting mixture I, is For preparing the material of soluble chemical fertilizer slow release device.
The method that the material prepares soluble chemical fertilizer slow release device, comprises the following steps:
Hollow cylinder is made Step 1: taking and being placed in the material for preparing soluble chemical fertilizer slow release device in mould Body, it is standby;Take to be placed in mould in the material for preparing soluble chemical fertilizer slow release device again and two solid cylinders be made, It is standby;Prepared solid cylinder diameter is identical with the interior diameter of hollow cylinder, and length is the 1/ of hollow cylinder body length 10-1/4;
Step 2: wrapping up rubber on prepared solid cylinder surface, obtain wrapping up the solid cylinder of rubber;Using The solid cylinder of rubber is wrapped up by hollow cylinder sealing two ends, that is, prepares soluble chemical fertilizer slow release device.
The application method of the soluble chemical fertilizer slow release device, comprises the following steps:
Step 1: according to the different dissolved fertilizer of different Plants types choices, it is big according to required selection fertilizer slow release device It is small;The solid cylinder of soluble chemical fertilizer slow release device wherein one end parcel rubber is removed, dissolved fertilizer is loaded empty Heart cylinder, sealing;
It is Step 2: the fertilizer slow release device equipped with dissolved fertilizer is vertical or lie low and be buried in the earth;Vertical embedment flowerpot Depth for soluble chemical fertilizer slow release device upper end under native table 1-2cm, lie low embedment flowerpot depth be native table under 1- 2cm;
Step 3: after 6-12 months, soluble chemical fertilizer slow release device is taken out, supplements fertilizer, can be according to the method described above Recycling.
Embodiment 1
A kind of material for being used to prepare soluble chemical fertilizer slow release device, it is characterised in that:Its raw material is by following weight The material composition of part:1 part of 100 parts of cement, 10 parts of perlite, 3 parts of cement blowing agent, 50 parts of water and anti-crack fiber.
The preparation method for being used to prepare the material of soluble chemical fertilizer slow release device, comprises the following steps:
Step 1: cement, perlite, cement blowing agent, water and anti-crack fiber are taken according to parts by weight, it is standby;
Step 2: by water intaking and cement blowing agent be placed in container, puddle uniformly, after thering are a large amount of foams to occur, add Cement and perlite, after being again stirring for 15min, add anti-crack fiber, stir 5 minutes, resulting mixture I, are as used to make The material of standby soluble chemical fertilizer slow release device.
The method that the material prepares soluble chemical fertilizer slow release device, comprises the following steps:
Hollow cylinder is made Step 1: taking and being placed in the material for preparing soluble chemical fertilizer slow release device in mould Body, it is standby;Take to be placed in mould in the material for preparing soluble chemical fertilizer slow release device again and two solid cylinders be made, It is standby;Prepared solid cylinder diameter is identical with the interior diameter of hollow cylinder, and length is the 1/ of hollow cylinder body length 10;
Step 2: wrapping up rubber on prepared solid cylinder surface, obtain wrapping up the solid cylinder of rubber;Using The solid cylinder of rubber is wrapped up by hollow cylinder sealing two ends, that is, prepares soluble chemical fertilizer slow release device.
The application method of the soluble chemical fertilizer slow release device, comprises the following steps:
Step 1: according to the different dissolved fertilizer of different Plants types choices, it is big according to required selection fertilizer slow release device It is small;The solid cylinder of soluble chemical fertilizer slow release device wherein one end parcel rubber is removed, dissolved fertilizer is loaded empty Heart cylinder, sealing;
It is Step 2: the fertilizer slow release device equipped with dissolved fertilizer is vertical or lie low and be buried in the earth;Vertical embedment flowerpot Depth for soluble chemical fertilizer slow release device upper end under native table 1cm, lie low embedment flowerpot depth be native table under 1cm;
Step 3: after 6 months, soluble chemical fertilizer slow release device is taken out, fertilizer is supplemented, can repeat according to the method described above Utilize.
Embodiment 2
A kind of material for being used to prepare soluble chemical fertilizer slow release device, it is characterised in that:Its raw material is by following weight The material composition of part:100 parts of cement, 20 parts of perlite, 7 parts of cement blowing agent, 70 parts of water and anti-crack fiber 1-3 parts.
The preparation method for being used to prepare the material of soluble chemical fertilizer slow release device, comprises the following steps:
Step 1: cement, perlite, cement blowing agent, water and anti-crack fiber are taken according to parts by weight, it is standby;
Step 2: by water intaking and cement blowing agent be placed in container, puddle uniformly, after thering are a large amount of foams to occur, add Cement and perlite, after being again stirring for 20min, add anti-crack fiber, stir 10 minutes, resulting mixture I, are as used to make The material of standby soluble chemical fertilizer slow release device.
The method that the material prepares soluble chemical fertilizer slow release device, comprises the following steps:
Hollow cylinder is made Step 1: taking and being placed in the material for preparing soluble chemical fertilizer slow release device in mould Body, it is standby;Take to be placed in mould in the material for preparing soluble chemical fertilizer slow release device again and two solid cylinders be made, It is standby;Prepared solid cylinder diameter is identical with the interior diameter of hollow cylinder, and length is the 1/ of hollow cylinder body length 4;
Step 2: wrapping up rubber on prepared solid cylinder surface, obtain wrapping up the solid cylinder of rubber;Using The solid cylinder of rubber is wrapped up by hollow cylinder sealing two ends, that is, prepares soluble chemical fertilizer slow release device.
The application method of the soluble chemical fertilizer slow release device, comprises the following steps:
Step 1: according to the different dissolved fertilizer of different Plants types choices, it is big according to required selection fertilizer slow release device It is small;The solid cylinder of soluble chemical fertilizer slow release device wherein one end parcel rubber is removed, dissolved fertilizer is loaded empty Heart cylinder, sealing;
It is Step 2: the fertilizer slow release device equipped with dissolved fertilizer is vertical or lie low and be buried in the earth;Vertical embedment flowerpot Depth for soluble chemical fertilizer slow release device upper end under native table 1-2cm, lie low embedment flowerpot depth be native table under 2cm;
Step 3: after 12 months, soluble chemical fertilizer slow release device is taken out, fertilizer is supplemented, can weigh according to the method described above It is multiple to utilize.
Embodiment 3
A kind of material for being used to prepare soluble chemical fertilizer slow release device, it is characterised in that:Its raw material is by following weight The material composition of part:2 parts of 100 parts of cement, 15 parts of perlite, 6 parts of cement blowing agent, 60 parts of water and anti-crack fiber.
The preparation method for being used to prepare the material of soluble chemical fertilizer slow release device, comprises the following steps:
Step 1: cement, perlite, cement blowing agent, water and anti-crack fiber are taken according to parts by weight, it is standby;
Step 2: by water intaking and cement blowing agent be placed in container, puddle uniformly, after thering are a large amount of foams to occur, add Cement and perlite, after being again stirring for 18min, add anti-crack fiber, stir 8 minutes, resulting mixture I, are as used to make The material of standby soluble chemical fertilizer slow release device.
The method that the material prepares soluble chemical fertilizer slow release device, comprises the following steps:
Hollow cylinder is made Step 1: taking and being placed in the material for preparing soluble chemical fertilizer slow release device in mould Body, it is standby;Take to be placed in mould in the material for preparing soluble chemical fertilizer slow release device again and two solid cylinders be made, It is standby;Prepared solid cylinder diameter is identical with the interior diameter of hollow cylinder, and length is the 1/ of hollow cylinder body length 8;
Step 2: wrapping up rubber on prepared solid cylinder surface, obtain wrapping up the solid cylinder of rubber;Using The solid cylinder of rubber is wrapped up by hollow cylinder sealing two ends, that is, prepares soluble chemical fertilizer slow release device.
The application method of the soluble chemical fertilizer slow release device, comprises the following steps:
Step 1: according to the different dissolved fertilizer of different Plants types choices, it is big according to required selection fertilizer slow release device It is small;The solid cylinder of soluble chemical fertilizer slow release device wherein one end parcel rubber is removed, dissolved fertilizer is loaded empty Heart cylinder, sealing;
It is Step 2: the fertilizer slow release device equipped with dissolved fertilizer is vertical or lie low and be buried in the earth;Vertical embedment flowerpot Depth for soluble chemical fertilizer slow release device upper end under native table 1.5cm, lie low embedment flowerpot depth be native table under 1.5 cm;
Step 3: after 8 months, soluble chemical fertilizer slow release device is taken out, fertilizer is supplemented, can repeat according to the method described above Utilize.

Claims (3)

1. a kind of preparation method of soluble chemical fertilizer slow release device, it is characterised in that comprise the following steps:
Step 1: take the material prepared described in soluble chemical fertilizer slow release device:100 parts of cement, perlite 10-20 parts, water Cement foaming agent 3-7 parts, water 50-70 parts and anti-crack fiber 1-3 parts, are placed in mould and hollow cylinder are made, standby;Take again It is placed in the material for preparing soluble chemical fertilizer slow release device in mould and two solid cylinders is made, it is standby;Prepared Solid cylinder diameter is identical with the interior diameter of hollow cylinder, and length is the 1/10-1/4 of hollow cylinder body length;
Step 2: wrapping up rubber on prepared solid cylinder surface, obtain wrapping up the solid cylinder of rubber;Using parcel Hollow cylinder sealing two ends are prepared soluble chemical fertilizer slow release device by the solid cylinder of rubber.
A kind of 2. preparation method of soluble chemical fertilizer slow release device as claimed in claim 1, it is characterised in that:Described For the preparation method for the material for preparing soluble chemical fertilizer slow release device, comprise the following steps:
Step 1: take 100 parts of cement according to parts by weight, perlite 10-20 parts, cement blowing agent 3-7 parts, water 50-70 parts and Anti-crack fiber 1-3 parts are standby;
Step 2: by water intaking and cement blowing agent be placed in container, puddle uniformly, after thering are a large amount of foams to occur, add cement And perlite, after being again stirring for 15-20min, anti-crack fiber is added, 5-10 minutes is stirred, resulting mixture I, is as used for Prepare the material of soluble chemical fertilizer slow release device.
3. the user of delayed release device prepared by the preparation method of soluble chemical fertilizer slow release device as claimed in claim 1 Method, it is characterised in that:Comprise the following steps:
Step 1: according to Plants types choice dissolved fertilizer, according to required selection fertilizer slow release device size;Remove solubleization The solid cylinder of fertilizer slow release device wherein one end parcel rubber is learned, dissolved fertilizer is loaded into hollow cylinder, sealed;
It is Step 2: the fertilizer slow release device equipped with dissolved fertilizer is vertical or lie low and be buried in the earth;The depth of vertical embedment flowerpot For soluble chemical fertilizer slow release device upper end under native table 1-2cm, lie low embedment flowerpot depth be native table under 1-2cm;
Step 3: after 6-12 months, soluble chemical fertilizer slow release device is taken out, supplements fertilizer.
CN201510636316.4A 2015-09-30 2015-09-30 A kind of preparation, application method and the material of soluble chemical fertilizer slow release device Expired - Fee Related CN105085095B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201510636316.4A CN105085095B (en) 2015-09-30 2015-09-30 A kind of preparation, application method and the material of soluble chemical fertilizer slow release device

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201510636316.4A CN105085095B (en) 2015-09-30 2015-09-30 A kind of preparation, application method and the material of soluble chemical fertilizer slow release device

Publications (2)

Publication Number Publication Date
CN105085095A CN105085095A (en) 2015-11-25
CN105085095B true CN105085095B (en) 2018-03-06

Family

ID=54566533

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201510636316.4A Expired - Fee Related CN105085095B (en) 2015-09-30 2015-09-30 A kind of preparation, application method and the material of soluble chemical fertilizer slow release device

Country Status (1)

Country Link
CN (1) CN105085095B (en)

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008068278A1 (en) * 2006-12-06 2008-06-12 Basf Se Plant substrate based on an open cell melamine-formaldehyde foam
CN102675891A (en) * 2012-05-28 2012-09-19 中国热带农业科学院橡胶研究所 Slow-release fertilizer pot and preparation and fertilizing method thereof
CN102860232A (en) * 2012-09-26 2013-01-09 江苏花海农业科技有限公司 Method for greening barren hills
CN102976667A (en) * 2012-08-21 2013-03-20 江苏百瑞吉新材料有限公司 Plant-growing concrete material
CN103524201A (en) * 2013-09-03 2014-01-22 黄河水利委员会黄河水利科学研究院 Composite material for vegetation restoration and preparation method thereof
CN103819156A (en) * 2014-02-27 2014-05-28 济南大学 Fertilizer efficiency slow release type plant-growing cementing material
CN203683407U (en) * 2014-02-18 2014-07-02 广西大学 Slow-release and controlled-release fertilizer shell
CN104140338A (en) * 2014-08-20 2014-11-12 济南大学 Sustained-release fertilizer suitable for planting concrete and preparation method of sustained-release fertilizer
CN104150799A (en) * 2014-08-23 2014-11-19 济南大学 Fertilizer efficiency slow-released type lightweight aggregate and preparation method thereof

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110314884A1 (en) * 2010-06-25 2011-12-29 Spence William B Combining beneficial ash and kiln dust to produce mineral lime

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008068278A1 (en) * 2006-12-06 2008-06-12 Basf Se Plant substrate based on an open cell melamine-formaldehyde foam
CN102675891A (en) * 2012-05-28 2012-09-19 中国热带农业科学院橡胶研究所 Slow-release fertilizer pot and preparation and fertilizing method thereof
CN102976667A (en) * 2012-08-21 2013-03-20 江苏百瑞吉新材料有限公司 Plant-growing concrete material
CN102860232A (en) * 2012-09-26 2013-01-09 江苏花海农业科技有限公司 Method for greening barren hills
CN103524201A (en) * 2013-09-03 2014-01-22 黄河水利委员会黄河水利科学研究院 Composite material for vegetation restoration and preparation method thereof
CN203683407U (en) * 2014-02-18 2014-07-02 广西大学 Slow-release and controlled-release fertilizer shell
CN103819156A (en) * 2014-02-27 2014-05-28 济南大学 Fertilizer efficiency slow release type plant-growing cementing material
CN104140338A (en) * 2014-08-20 2014-11-12 济南大学 Sustained-release fertilizer suitable for planting concrete and preparation method of sustained-release fertilizer
CN104150799A (en) * 2014-08-23 2014-11-19 济南大学 Fertilizer efficiency slow-released type lightweight aggregate and preparation method thereof

Also Published As

Publication number Publication date
CN105085095A (en) 2015-11-25

Similar Documents

Publication Publication Date Title
CN105418039B (en) A kind of efficiency slow release type porous ecological concrete and preparation method thereof
US20220267228A1 (en) Solid waste-based porous materials, methods for preparing the same, and methods of ecological restoration of coal gangue hills by applying the same
JPS6023806B2 (en) Polymerized soil with growing plants and method of its formation
CN105061054A (en) Coated sustained-release fertilizer and production method thereof
CN104557278A (en) Method for manufacturing chemical fertilizer
CN107056177B (en) A kind of composite light aggregate eco-cement concrete floating bed and preparation method thereof
CN103798112B (en) The preparation method of intelligent nutrition matrix
CN104860772B (en) A kind of haydite flower nutrition cultivation matrix and preparation method thereof
CN105085095B (en) A kind of preparation, application method and the material of soluble chemical fertilizer slow release device
EP1099368A3 (en) Plant container and method of manufacture
CN207632726U (en) Biodegradable floral special-purpose fertilizer charge bar
CN105130715B (en) A kind of fertilizer for pot-culture flowers slow release device and its preparation and application
CN102336585B (en) Compound foamed concrete and floating bed
US3110129A (en) Method of improving the soil
CN105129997B (en) A kind of preparation method of lightweight concrete for plant growth floating bed
US20130263502A1 (en) Formulations for watering plants
CN103539516B (en) Method for preparing slow-controlled release fertilizer
US20080250713A1 (en) Liquid Storage Means For Supplying Plants
CN106588267A (en) Fertilizer coating composition
CN112919959A (en) Preparation method, product, equipment and application of fertilizer storage ceramsite
CN108371051A (en) A kind of aquatic plant fertilizer
CN104584939A (en) Mushroom dreg seedling growing nutrition bowl and manufacturing method thereof
CN109020606A (en) A kind of jardiniere for the fertilizer being sustained the bacterium containing EM
CN109121831A (en) A kind of adjusting humidity degradative flower bowl and preparation method thereof
JPH0733569A (en) Multi-layered capsule for soil-improver and fertilizer

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into 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: 20180306

Termination date: 20180930

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