Water-absorbing and water-retaining multi-nutrient biodegradable polymeric slow/controlled release fertilizer having a semi-interpenetrating network structure
10865161 ยท 2020-12-15
Assignee
Inventors
Cpc classification
C05B17/00
CHEMISTRY; METALLURGY
C08F292/00
CHEMISTRY; METALLURGY
C05G3/40
CHEMISTRY; METALLURGY
C08F220/06
CHEMISTRY; METALLURGY
C05B7/00
CHEMISTRY; METALLURGY
C08F220/06
CHEMISTRY; METALLURGY
C05B19/00
CHEMISTRY; METALLURGY
C08F292/00
CHEMISTRY; METALLURGY
International classification
C05B17/00
CHEMISTRY; METALLURGY
C05G3/40
CHEMISTRY; METALLURGY
C05B7/00
CHEMISTRY; METALLURGY
C05B19/00
CHEMISTRY; METALLURGY
C08F292/00
CHEMISTRY; METALLURGY
Abstract
This disclosure relates to water-absorbing and slow/controlled release fertilizer, in particular to a water-absorbing and water-retaining multi-nutrient biodegradable polymeric slow/controlled release fertilizer having a semi-interpenetrating network structure, and preparation methods thereof. The method can comprises the steps of: reacting formaldehyde with urea to obtain a hydroxymethyl urea solution; adding acrylic acid and acrylamide monomers into another reactor, and adding a KOH solution to adjust the neutralization degree of acrylic acid, then adding one of inorganic clay, pretreated crop straw or cellulose, then adding initiator, monopotassium phosphate and the prepared hydroxymethyl urea solution sequentially; allowing to react at temperature after being mixed uniformly to obtain a viscous product; and granulating the viscous product and oven drying the same to obtain the fertilizer. The fertilizer prepared according to the present invention has strong water-absorbing and water-retaining capacity, and an excellent slow release performance for nitrogen, phosphorus and potassium contained as nutrients.
Claims
1. A water-absorbing and water-retaining multi-nutrient biodegradable polymeric slow/controlled release fertilizer having a semi-interpenetrating network structure, wherein the fertilizer comprises a high polymer having a semi-interpenetrating network structure, said semi-interpenetrating network structure of the high polymer being such that a polymeric slow/controlled release fertilizer (PRF) molecular chain is interposed in a composite water-absorbing resin network; wherein said composite water-absorbing resin is of a three-dimensional spatial network structure formed by graft copolymerization of acrylic acid and acrylamide with inorganic clay or pretreated crop straw or cellulose under the action of an initiator and a crosslinking agent, wherein the PRF is the reaction product of hydroxymethyl urea and monopotassium phosphate, and wherein the semi-interpenetrating network structure is formed through simultaneous preparation of the composite water-absorbing resin and PRF in one reaction system.
2. The water-absorbing and water-retaining multi-nutrient biodegradable polymeric slow/controlled release fertilizer having a semi-interpenetrating network structure according to claim 1, wherein the fertilizer further comprises a polymeric slow/controlled release fertilizer (PRF) as the reaction product of hydroxymethyl urea and monopotassium phosphate that separates itself from the composite water-absorbing resin three-dimensional spatial network structure and aggregates into a monophasic structure.
3. A method for preparing a water-absorbing and water-retaining multi-nutrient biodegradable polymeric slow/controlled release fertilizer having a semi-interpenetrating network structure, wherein said method comprises the steps of: (1) adding formaldehyde and urea respectively into a first reactor, adjusting the resultant system to pH=8 with a 5% KOH solution, and reacting the same at 40 C. for 2 h to obtain a hydroxymethyl urea solution; (2) adding acrylic acid and acrylamide into a second reactor, and adding a 20 mass % KOH solution to adjust the neutralization degree of acrylic acid monomer to 20%-100%; adding inorganic clay, pretreated crop straw or cellulose; and then adding monopotassium phosphate, an initiator and the hydroxymethyl urea solution prepared in step (1) sequentially, mixing them under an ice bath for 30 min, warming the resultant mixture to 55 C. and then reacting the same under an atmosphere of nitrogen for 4 h to obtain a viscous product; and (3) granulating the obtained viscous product and oven drying the same to obtain a water-absorbing and water-retaining multi-nutrient biodegradable polymeric slow/controlled release fertilizer having a semi-interpenetrating network structure.
4. The method for preparing a water-absorbing and water-retaining multi-nutrient biodegradable polymeric slow/controlled release fertilizer having a semi-interpenetrating network structure according to claim 3, wherein the molar ratio of formaldehyde to urea is 1:1.2-2.
5. The method for preparing a water-absorbing and water-retaining multi-nutrient biodegradable polymeric slow/controlled release fertilizer having a semi-interpenetrating network structure according to claim 3, wherein the pretreatment of said crop straw comprises the steps of: weighing an amount of crop straw powder, immersing it in distilled water, soaking it at 60 C. for 12 h to produce a crop straw powder suspension, and then filtering the crop straw powder suspension to obtain a crop straw powder filter cake, placing the filter cake into a solution consisting of 24% KOH and 1% NaBH.sub.4, stirring the same for 3 h to produce a second crop straw powder suspension, and then filtering the second crop straw powder suspension to obtain a second crop straw powder filter cake, then washing the second crop straw powder filter cake with distilled water repeatedly until the filtrate is neutral to produce a washed crop straw powder filter cake, and oven drying the washed crop straw powder filter cake to obtain a pretreated crop straw.
6. The method for preparing a water-absorbing and water-retaining multi-nutrient biodegradable polymeric slow/controlled release fertilizer having a semi-interpenetrating network structure according to claim 3, wherein the mass ratio of acrylic acid to acrylamide to inorganic clay in step (2) is (2-10):1:(0.2-1).
7. The method for preparing a water-absorbing and water-retaining multi-nutrient biodegradable polymeric slow/controlled release fertilizer having a semi-interpenetrating network structure according to claim 3, wherein in step (2), said monopotassium phosphate, initiator and hydroxymethyl urea solution are added in an amount of 0-10%, 0.1%-1% and 0-100% of the total mass of acrylic acid and acrylamide respectively, and the addition amount of neither monopotassium phosphate nor hydroxymethyl urea solution is 0.
8. The method for preparing a water-absorbing and water-retaining multi-nutrient biodegradable polymeric slow/controlled release fertilizer having a semi-interpenetrating network structure according to claim 3, wherein said inorganic clay is attapulgite, kaolin, diatomite, mica, bentonite, hydrotalcite, stilbite, illite or rectorite; said crop straw is wheat straw, rice straw, maize straw or sorghum straw; and said cellulose is carboxymethyl cellulose, hydroxyethyl cellulose or cellulose xanthogenate.
9. The method for preparing a water-absorbing and water-retaining multi-nutrient biodegradable polymeric slow/controlled release fertilizer having a semi-interpenetrating network structure according to claim 3, wherein said initiator is hydrogen peroxide, potassium persulfate, sodium persulfate, ammonium persulfate, ceric nitrate, a mixture of hydrogen peroxide and ferrous sulfate, a mixture of persulfate and sodium bisulfite, a mixture of persulfate and sodium sulfite, or L-ascorbic acid.
10. The method for preparing a water-absorbing and water-retaining multi-nutrient biodegradable polymeric slow/controlled release fertilizer having a semi-interpenetrating network structure according to claim 3, wherein the mass ratio of acrylic acid to acrylamide to pretreated crop straw in step (2) is (2-10):1:(0.2-1).
11. The method for preparing a water-absorbing and water-retaining multi-nutrient biodegradable polymeric slow/controlled release fertilizer having a semi-interpenetrating network structure according to claim 3, wherein the mass ratio of acrylic acid to acrylamide to cellulose in step (2) is (2-10):1:(0.2-1).
Description
DESCRIPTION OF THE DRAWINGS
(1) The foregoing aspects and many of the attendant advantages of this invention will become more readily appreciated as the same become better understood by reference to the following detailed description, when taken in conjunction with the accompanying drawings, wherein:
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DETAILED DESCRIPTION
(13) The percentage concentration (%) not specifically stated throughout the specification refers to a mass fraction w/w (percentage by mass concentration).
(14) A water-absorbing and water-retaining multi-nutrient biodegradable polymeric slow/controlled release fertilizer having a semi-interpenetrating network structure, comprising a high polymer having a semi-interpenetrating network structure, said semi-interpenetrating network structure of the high polymer being such that a polymeric slow/controlled release fertilizer (PRF) molecular chain is interposed in a composite water-absorbing resin network;
(15) wherein said composite water-absorbing resin is of a three-dimensional spatial network structure formed by graft copolymerization of acrylic acid and acrylamide with inorganic clay, pretreated crop straw or cellulose backbone under the action of an initiator and a crosslinking agent.
(16) In addition, said water-absorbing and water-retaining multi-nutrient biodegradable polymeric slow/controlled release fertilizer having a semi-interpenetrating network structure further comprises a polymeric slow/controlled release fertilizer (PRF) that separates itself from the composite water-absorbing resin three-dimensional spatial network structure and aggregates into a monophasic structure.
(17) Further, said water-absorbing and water-retaining multi-nutrient biodegradable polymeric slow/controlled release fertilizer having a semi-interpenetrating network structure further comprises inorganic clay, pretreated crop straw or cellulose that separates itself from the composite water-absorbing resin three-dimensional spatial network structure.
(18) The present invention provides a method for preparing a water-absorbing and water-retaining multi-nutrient biodegradable polymeric slow/controlled release fertilizer having a semi-interpenetrating network structure, comprising the steps of:
(19) (1) adding formaldehyde and urea respectively into a first reactor, adjusting the resultant system to pH=8 with a 5% KOH solution, and reacting the same at 40 C. for 2 h to obtain a hydroxymethyl urea solution;
(20) (2) adding acrylic acid and acrylamide into a second reactor, and adding a 20 mass % KOH solution to adjust the neutralization degree of acrylic acid monomer to 20% to 100%; adding one of inorganic clay, pretreated crop straw or cellulose; and then adding monopotassium phosphate, an initiator and the hydroxymethyl urea solution prepared in step (1) sequentially, mixing them under an ice bath for 30 min, warming the resultant mixture to 55 C. and then reacting the same under an atmosphere of nitrogen for 4 h to obtain a viscous product;
(21) (3) granulating the obtained viscous product and oven drying the same to obtain a water-absorbing and water-retaining multi-nutrient biodegradable polymeric slow/controlled release fertilizer having a semi-interpenetrating network structure.
(22) The above neutralization degree of acrylic acid monomer can be selected to be 20%, 40%, 60%, 80% or 100%. However, the neutralization degree is preferably 80% in view of the water absorption of the copolymer.
(23) Preferably, the molar ratio of formaldehyde to urea is 1:1.2 to 2. For example, it can be selected to be 1:1.2, 1:1.5 or 1:2.
(24) Preferably, in step (2), the mass ratio of acrylic acid to acrylamide to inorganic clay, pretreated crop straw or cellulose is (2 to 10):1:(0.2 to 1). For example, it can be selected to be 2:1:0.2, 2:1:1, 10:1:1, or 10:1:0.2.
(25) Specifically, in step (2), said monopotassium phosphate, initiator and hydroxymethyl urea solution are added in an amount of 0 to 10%, 0.1% to 1% and 0 to 100% of the total mass of acrylic acid and acrylamide respectively, and the addition amount of neither monopotassium phosphate nor hydroxymethyl urea solution is 0. For example, monopotassium phosphate constitutes 0.1%, 1%, 5% or 10% of the total mass of acrylic acid and acrylamide; the initiator constitutes 0.1%, 0.55% or 1% of the total mass of acrylic acid and acrylamide; and hydroxymethyl urea solution constitutes 0.1%, 10%, 20%, 50% or 100% of the total mass of acrylic acid and acrylamide.
(26) Specifically, said inorganic clay is any one of attapulgite, kaolin, diatomite, mica, bentonite, hydrotalcite, stilbite, illite and rectorite. Said crop straw is any one of wheat straw, rice straw, maize straw and sorghum straw. Said cellulose is any one of carboxymethyl cellulose, hydroxyethyl cellulose and cellulose xanthogenate.
(27) In a specific embodiment, said initiator is any one of hydrogen peroxide, potassium persulfate, sodium persulfate, ammonium persulfate, ceric nitrate, a mixture of hydrogen peroxide and ferrous sulfate, a mixture of persulfate and sodium bisulfite, a mixture of persulfate and sodium sulfite, and L-ascorbic acid.
(28) In order to illustrate the technical content of the present invention more clearly, the following specific Examples are provided.
Example 1
(29) A method for preparing an inorganic clay-based water-absorbing and water-retaining multi-nutrient biodegradable polymeric slow/controlled release fertilizer having a semi-interpenetrating network structure, comprising the steps of:
(30) (1) adding 4.06 g of formaldehyde and 6 g of urea respectively into a first reactor, adjusting the resultant system to pH=8 with a 5% KOH solution, and reacting the same at 40 C. for 2 h to obtain a hydroxymethyl urea solution;
(31) (2) adding 5 g of acrylic acid, 2 g of acrylamide and 0.7 g of diatomite into a second reactor, and adding a 20 mass % KOH solution to adjust the neutralization degree of acrylic acid to 80%; and then adding 0.5 g of monopotassium phosphate, 0.021 g of ammonium persulfate and 12 g of the hydroxymethyl urea solution prepared in step (1), mixing them under an ice bath for 30 min, warming the resultant mixture to 55 C. and then reacting the same under an atmosphere of nitrogen for 4 h to obtain a viscous product; and
(32) (3) granulating the obtained viscous product and oven drying the same to obtain a diatomite-based water-absorbing and water-retaining multi-nutrient biodegradable polymeric slow/controlled release fertilizer having a semi-interpenetrating network structure.
(33) In the resulting inorganic diatomite-based water-absorbing and water-retaining multi-nutrient biodegradable polymeric slow/controlled release fertilizer having a semi-interpenetrating network structure, the content of nitrogen is 35.74%, the content of phosphorus is 1.07% in terms of P.sub.2O.sub.5, the content of potassium is 10.22% in terms of K.sub.2O; and the water absorbency in tap water is 86 g/g.
Example 2
(34) A method for preparing an inorganic clay-based water-absorbing and water-retaining multi-nutrient biodegradable polymeric slow/controlled release fertilizer having a semi-interpenetrating network structure, comprising the steps of:
(35) (1) adding 4.06 g of formaldehyde and 6 g of urea respectively into a first reactor, adjusting the resultant system to pH=8 with a 5% KOH solution, and reacting the same at 40 C. for 2 h to obtain a hydroxymethyl urea solution;
(36) (2) adding 5 g of acrylic acid, 2 g of acrylamide and 0.7 g of attapulgite into a second reactor, and adding a 20 mass % KOH solution to adjust the neutralization degree of acrylic acid to 80%; and then adding 0.5 g of monopotassium phosphate, 0.021 g of ammonium persulfate and 12 g of the hydroxymethyl urea solution prepared in step (1), mixing them under an ice bath for 30 min, warming the resultant mixture to 55 C. and then reacting the same under an atmosphere of nitrogen for 4 h to obtain a viscous product; and
(37) (3) granulating the obtained viscous product and oven drying the same to obtain a attapulgite-based water-retaining multi-nutrient biodegradable polymeric slow/controlled release fertilizer having a semi-interpenetrating network structure.
(38) In the resulting attapulgite-based water-absorbing and water-retaining multi-nutrient biodegradable polymeric slow/controlled release fertilizer having a semi-interpenetrating network structure, the content of nitrogen is 35.68%, the content of phosphorus is 1.17% in terms of P.sub.2O.sub.5, the content of potassium is 13.70% in terms of K.sub.2O; and the water absorbency in tap water is 45 g/g.
Example 3
(39) A method for preparing an inorganic clay-based water-absorbing and water-retaining multi-nutrient biodegradable polymeric slow/controlled release fertilizer having a semi-interpenetrating network structure, comprising the steps of:
(40) (1) adding 4.06 g of formaldehyde and 6 g of urea respectively into a first reactor, adjusting the resultant system to pH=8 with a 5% KOH solution, and reacting the same at 40 C. for 2 h to obtain a hydroxymethyl urea solution;
(41) (2) adding 5 g of acrylic acid, 2 g of acrylamide and 0.7 g of kaolin into a second reactor, and adding a 20 mass % KOH solution to adjust the neutralization degree of acrylic acid to 80%; and then adding 0.5 g of monopotassium phosphate, 0.021 g of ammonium persulfate and 12 g of the hydroxymethyl urea solution prepared in step (1), mixing them under an ice bath for 30 min, warming the resultant mixture to 55 C. and then reacting the same under an atmosphere of nitrogen for 4 h to obtain a viscous product; and
(42) (3) granulating the obtained viscous product and oven drying the same to obtain a kaolin-based water-absorbing and water-retaining multi-nutrient biodegradable polymeric slow/controlled release fertilizer having a semi-interpenetrating network structure.
(43) In the resulting kaolin-based water-absorbing and water-retaining multi-nutrient biodegradable polymeric slow/controlled release fertilizer having a semi-interpenetrating network structure, the content of nitrogen is 34.81%, the content of phosphorus is 1.31% in terms of P.sub.2O.sub.5, the content of potassium is 11.32% in terms of K.sub.2O; and the water absorbency in tap water is 70 g/g.
Example 4
(44) A method for preparing an inorganic clay-based water-absorbing and water-retaining multi-nutrient biodegradable polymeric slow/controlled release fertilizer having a semi-interpenetrating network structure, comprising the steps of:
(45) (1) adding 4.06 g of formaldehyde and 6 g of urea respectively into a first reactor, adjusting the resultant system to pH=8 with a 5% KOH solution, and reacting the same at 40 C. for 2 h to obtain a hydroxymethyl urea solution;
(46) (2) adding 5 g of acrylic acid, 2 g of acrylamide and 0.7 g of mica into a second reactor, and adding a 20 mass % KOH solution to adjust the neutralization degree of acrylic acid to 80%; and then adding 0.5 g of monopotassium phosphate, 0.021 g of ammonium persulfate and 12 g of the hydroxymethyl urea solution prepared in step (1), mixing them under an ice bath for 30 min, warming the resultant mixture to 55 C. and then reacting the same under an atmosphere of nitrogen for 4 h to obtain a viscous product; and
(47) (3) granulating the obtained viscous product and oven drying the same to obtain a mica-based water-absorbing and water-retaining multi-nutrient biodegradable polymeric slow/controlled release fertilizer having a semi-interpenetrating network structure.
(48) In the resulting mica-based water-absorbing and water-retaining multi-nutrient biodegradable polymeric slow/controlled release fertilizer having a semi-interpenetrating network structure, the content of nitrogen is 34.90%, the content of phosphorus is 0.76% in terms of P.sub.2O.sub.5, the content of potassium is 9.53% in terms of K.sub.2O; and the water absorbency in tap water is 70 g/g.
Example 5
(49) A method for preparing a clay-based water-absorbing and water-retaining multi-nutrient biodegradable polymeric slow/controlled release fertilizer having a semi-interpenetrating network structure, comprising the steps of:
(50) (1) adding 4.06 g of formaldehyde and 6 g of urea respectively into a first reactor, adjusting the resultant system to pH=8 with a 5% KOH solution, and reacting the same at 40 C. for 2 h to obtain a hydroxymethyl urea solution;
(51) (2) adding 5 g of acrylic acid, 2 g of acrylamide and 0.7 g of diatomite into a second reactor, and adding a 20 mass % KOH solution to adjust the neutralization degree of acrylic acid to 80%; and then adding 0.5 g of monopotassium phosphate, 0.021 g of ammonium persulfate and 12 g of the hydroxymethyl urea solution prepared in step (1), mixing them under an ice bath for 30 min, warming the resultant mixture to 55 C. and then reacting the same under an atmosphere of nitrogen for 4 h to obtain a viscous product; and
(52) (3) granulating the obtained viscous product and oven drying the same to obtain a montmorillonite-based water-absorbing and water-retaining multi-nutrient biodegradable polymeric slow/controlled release fertilizer having a semi-interpenetrating network structure.
(53) In the resulting montmorillonite-based water-retaining multi-nutrient biodegradable polymeric slow/controlled release fertilizer having a semi-interpenetrating network structure, the content of nitrogen is 35.86%, the content of phosphorus is 0.96% in terms of P.sub.2O.sub.5, the content of potassium is 16.52% in terms of K.sub.2O; and the water absorbency in tap water is 58 g/g.
Example 6
(54) A method for preparing an inorganic clay-based water-absorbing and water-retaining multi-nutrient biodegradable polymeric slow/controlled release fertilizer having a semi-interpenetrating network structure, comprising the steps of:
(55) (1) adding 4.06 g of formaldehyde and 6 g of urea respectively into a first reactor, adjusting the resultant system to pH=8 with a 5% KOH solution, and reacting the same at 40 C. for 2 h to obtain a hydroxymethyl urea solution;
(56) (2) adding 5 g of acrylic acid, 2 g of acrylamide and 0.7 g of kaolin into a second reactor, and adding a 20 mass % KOH solution to adjust the neutralization degree of acrylic acid to 80%; and then adding 1 g of monopotassium phosphate, 0.021 g of ammonium persulfate and 12 g of the hydroxymethyl urea solution prepared in step (1), mixing them under an ice bath for 30 min, warming the resultant mixture to 55 C. and then reacting the same under an atmosphere of nitrogen for 4 h to obtain a viscous product; and
(57) (3) granulating the obtained viscous product and oven drying the same to obtain a kaolin-based water-absorbing and water-retaining multi-nutrient biodegradable polymeric slow/controlled release fertilizer having a semi-interpenetrating network structure.
(58) In the resulting kaolin-based water-absorbing and water-retaining multi-nutrient biodegradable polymeric slow/controlled release fertilizer having a semi-interpenetrating network structure, the content of nitrogen is 29.73%, the content of phosphorus is 2.35% in terms of P.sub.2O.sub.5, the content of potassium is 18.52% in terms of K.sub.2O; and the water absorbency in tap water is 39 g/g.
Example 7
(59) A method for preparing an inorganic clay-based water-absorbing and water-retaining multi-nutrient biodegradable polymeric slow/controlled release fertilizer having a semi-interpenetrating network structure, comprising the steps of:
(60) (1) adding 2.03 g of formaldehyde and 3 g of urea respectively into a first reactor, adjusting the resultant system to pH=8 with a 5% KOH solution, and reacting the same at 40 C. for 2 h to obtain a hydroxymethyl urea solution;
(61) (2) adding 5 g of acrylic acid, 2 g of acrylamide and 0.7 g of kaolin into a second reactor, and adding a 20 mass % KOH solution to adjust the neutralization degree of acrylic acid to 80%; and then adding 0.5 g of monopotassium phosphate, 0.021 g of ammonium persulfate and 6 g of the hydroxymethyl urea solution prepared in step (1), mixing them under an ice bath for 30 min, warming the resultant mixture to 55 C. and then reacting the same under an atmosphere of nitrogen for 4 h to obtain a viscous product; and
(62) (3) granulating the obtained viscous product and oven drying the same to obtain a kaolin-based water-absorbing and water-retaining multi-nutrient biodegradable polymeric slow/controlled release fertilizer having a semi-interpenetrating network structure.
(63) In the resulting kaolin-based water-absorbing and water-retaining multi-nutrient biodegradable polymeric slow/controlled release fertilizer having a semi-interpenetrating network structure, the content of nitrogen is 21.86%, the content of phosphorus is 1.94% in terms of P.sub.2O.sub.5, the content of potassium is 13.37% in terms of K.sub.2O; and the water absorbency in tap water is 126 g/g.
Example 8
(64) A method for preparing a crop straw-based water-absorbing and water-retaining multi-nutrient biodegradable polymeric slow/controlled release fertilizer having a semi-interpenetrating network structure, comprising the steps of:
(65) (1) adding 6.70 g of formaldehyde and 6 g of urea respectively into a first reactor, adjusting the resultant system to pH=8 with a 5% KOH solution, and reacting the same at 40 C. for 2 h to obtain a hydroxymethyl urea solution;
(66) (2) adding 5 g of acrylic acid, 2 g of acrylamide and 0.7 g of treated crop straw powder into a second reactor, and adding a 20 mass % KOH solution to adjust the neutralization degree of acrylic acid to 80%; and then adding 0.5 g of monopotassium phosphate, 0.021 g of ammonium persulfate and 12 g of the hydroxymethyl urea solution prepared in step (1), mixing them under an ice bath for 30 min, warming the resultant mixture to 55 C. and then reacting the same under an atmosphere of nitrogen for 4 h to obtain a viscous product; and
(67) (3) granulating the obtained viscous product and oven drying the same to obtain a crop straw-based water-absorbing and water-retaining multi-nutrient biodegradable polymeric slow/controlled release fertilizer having a semi-interpenetrating network structure.
(68) In the resulting crop straw-based water-absorbing and water-retaining multi-nutrient biodegradable polymeric slow/controlled release fertilizer having a semi-interpenetrating network structure, the content of nitrogen is 29.30%, the content of phosphorus is 0.92% in terms of P.sub.2O.sub.5, the content of potassium is 11.76% in terms of K.sub.2O; and the water absorbency in tap water is 26 g/g.
Example 9
(69) A method for preparing a crop straw-based water-absorbing and water-retaining multi-nutrient biodegradable polymeric slow/controlled release fertilizer having a semi-interpenetrating network structure, comprising the steps of:
(70) (1) adding 4.06 g of formaldehyde and 6 g of urea respectively into a first reactor, adjusting the resultant system to pH=8 with a 5% KOH solution, and reacting the same at 40 C. for 2 h to obtain a hydroxymethyl urea solution;
(71) (2) adding 5.6 g of acrylic acid, 1.4 g of acrylamide and 0.7 g of treated crop straw powder into a second reactor, and adding a 20 mass % KOH solution to adjust the neutralization degree of acrylic acid to 80%; and then adding 0.5 g of monopotassium phosphate, 0.021 g of ammonium persulfate and 12 g of the hydroxymethyl urea solution prepared in step (1), mixing them under an ice bath for 30 min, warming the resultant mixture to 55 C. and then reacting the same under an atmosphere of nitrogen for 4 h to obtain a viscous product; and
(72) (3) granulating the obtained viscous product and oven drying the same to obtain a crop straw-based water-absorbing and water-retaining multi-nutrient biodegradable polymeric slow/controlled release fertilizer having a semi-interpenetrating network structure.
(73) In the resulting crop straw-based water-absorbing and water-retaining multi-nutrient biodegradable polymeric slow/controlled release fertilizer having a semi-interpenetrating network structure, the content of nitrogen is 32.80%, the content of phosphorus is 0.98% in terms of P.sub.2O.sub.5, the content of potassium is 12.60% in terms of K.sub.2O; and the water absorbency in tap water is 42 g/g.
Example 10
(74) A method for preparing a crop straw-based water-absorbing and water-retaining multi-nutrient biodegradable polymeric slow/controlled release fertilizer having a semi-interpenetrating network structure, comprising the steps of:
(75) (1) adding 4.06 g of formaldehyde and 6 g of urea respectively into a first reactor, adjusting the resultant system to pH=8 with a 5% KOH solution, and reacting the same at 40 C. for 2 h to obtain a hydroxymethyl urea solution;
(76) (2) adding 5 g of acrylic acid, 2 g of acrylamide and 0.7 g of treated crop straw powder into a second reactor, and adding a 20 mass % KOH solution to adjust the neutralization degree of acrylic acid to 80%; and then adding 0.5 g of monopotassium phosphate, 0.021 g of ammonium persulfate and 12 g of the hydroxymethyl urea solution prepared in step (1), mixing them under an ice bath for 30 min, warming the resultant mixture to 55 C. and then reacting the same under an atmosphere of nitrogen for 4 h to obtain a viscous product; and
(77) (3) granulating the obtained viscous product and oven drying the same to obtain a crop straw-based water-absorbing and water-retaining multi-nutrient biodegradable polymeric slow/controlled release fertilizer having a semi-interpenetrating network structure.
(78) In the resulting crop straw-based water-absorbing and water-retaining multi-nutrient biodegradable polymeric slow/controlled release fertilizer having a semi-interpenetrating network structure, the content of nitrogen is 33.20%, the content of phosphorus is 0.94% in terms of P.sub.2O.sub.5, the content of potassium is 13.62% in terms of K.sub.2O; and the water absorbency in tap water is 46 g/g.
Example 11
(79) A method for preparing a crop straw-based water-absorbing and water-retaining multi-nutrient biodegradable polymeric slow/controlled release fertilizer having a semi-interpenetrating network structure, comprising the steps of:
(80) (1) adding 4.06 g of formaldehyde and 6 g of urea respectively into a first reactor, adjusting the resultant system to pH=8 with a 5% KOH solution, and reacting the same at 40 C. for 2 h to obtain a hydroxymethyl urea solution;
(81) (2) adding 5 g of acrylic acid, 2 g of acrylamide and 1.4 g of treated crop straw powder into a second reactor, and adding a 20 mass % KOH solution to adjust the neutralization degree of acrylic acid to 80%; and then adding 0.5 g of monopotassium phosphate, 0.021 g of ammonium persulfate and 12 g of the hydroxymethyl urea solution prepared in step (1), mixing them under an ice bath for 30 min, warming the resultant mixture to 55 C. and then reacting the same under an atmosphere of nitrogen for 4 h to obtain a viscous product; and
(82) (3) granulating the obtained viscous product and oven drying the same to obtain a crop straw-based water-absorbing and water-retaining multi-nutrient biodegradable polymeric slow/controlled release fertilizer having a semi-interpenetrating network structure.
(83) In the resulting crop straw-based water-absorbing and water-retaining multi-nutrient biodegradable polymeric slow/controlled release fertilizer having a semi-interpenetrating network structure, the content of nitrogen is 26.43%, the content of phosphorus is 0.82% in terms of P.sub.2O.sub.5, the content of potassium is 9.64% in terms of K.sub.2O; and the water absorbency in tap water is 38 g/g.
Example 12
(84) A method for preparing a crop straw-based water-absorbing and water-retaining multi-nutrient biodegradable polymeric slow/controlled release fertilizer having a semi-interpenetrating network structure, comprising the steps of:
(85) (1) adding 4.06 g of formaldehyde and 6 g of urea respectively into a first reactor, adjusting the resultant system to pH=8 with a 5% KOH solution, and reacting the same at 40 C. for 2 h to obtain a hydroxymethyl urea solution;
(86) (2) adding 5 g of acrylic acid, 2 g of acrylamide and 0.7 g of treated crop straw powder into a second reactor, and adding a 20 mass % KOH solution to adjust the neutralization degree of acrylic acid to 80%; and then adding 0.8 g of monopotassium phosphate, 0.021 g of ammonium persulfate and 12 g of the hydroxymethyl urea solution prepared in step (1), mixing them under an ice bath for 30 min, warming the resultant mixture to 55 C. and then reacting the same under an atmosphere of nitrogen for 4 h to obtain a viscous product; and
(87) (3) granulating the obtained viscous product and oven drying the same to obtain a crop straw-based water-absorbing and water-retaining multi-nutrient biodegradable polymeric slow/controlled release fertilizer having a semi-interpenetrating network structure.
(88) In the resulting crop straw-based water-absorbing and water-retaining multi-nutrient biodegradable polymeric slow/controlled release fertilizer having a semi-interpenetrating network structure, the content of nitrogen is 30.65%, the content of phosphorus is 1.48% in terms of P.sub.2O.sub.5, the content of potassium is 16.32% in terms of K.sub.2O; and the water absorbency in tap water is 34 g/g.
Example 13
(89) A method for preparing a crop straw-based water-absorbing and water-retaining multi-nutrient biodegradable polymeric slow/controlled release fertilizer having a semi-interpenetrating network structure, comprising the steps of:
(90) (1) adding 4.06 g of formaldehyde and 6 g of urea respectively into a first reactor, adjusting the resultant system to pH=8 with a 5% KOH solution, and reacting the same at 40 C. for 2 h to obtain a hydroxymethyl urea solution;
(91) (2) adding 5 g of acrylic acid, 2 g of acrylamide and 0.7 g of treated crop straw powder into a second reactor, and adding a 20 mass % KOH solution to adjust the neutralization degree of acrylic acid to 80%; and then adding 1 g of monopotassium phosphate, 0.021 g of ammonium persulfate and 12 g of hydroxymethyl urea solution prepared in step (1), mixing them under an ice bath for 30 min, warming the resultant mixture to 55 C. and then reacting the same under an atmosphere of nitrogen for 4 h to obtain a viscous product; and
(92) (3) granulating the obtained viscous product and oven drying the same to obtain a crop straw-based water-absorbing and water-retaining multi-nutrient biodegradable polymeric slow/controlled release fertilizer having a semi-interpenetrating network structure.
(93) In the resulting crop straw-based water-absorbing and water-retaining multi-nutrient biodegradable polymeric slow/controlled release fertilizer having a semi-interpenetrating network structure, the content of nitrogen is 30.19%, the content of phosphorus is 1.97% in terms of P.sub.2O.sub.5, the content of potassium is 19.83% in terms of K.sub.2O; and the water absorbency in tap water is 27 g/g.
Example 14
(94) A method for preparing a crop straw-based water-absorbing and water-retaining multi-nutrient biodegradable polymeric slow/controlled release fertilizer having a semi-interpenetrating network structure, comprising the steps of:
(95) (1) adding 1.35 g of formaldehyde and 2 g of urea respectively into a first reactor, adjusting the resultant system to pH=8 with a 5% KOH solution, and reacting the same at 40 C. for 2 h to obtain a hydroxymethyl urea solution;
(96) (2) adding 5 g of acrylic acid, 2 g of acrylamide and 0.7 g of treated crop straw powder into a second reactor, and adding a 20 mass % KOH solution to adjust the neutralization degree of acrylic acid to 80%; and then adding 0.5 g of monopotassium phosphate, 0.021 g of ammonium persulfate and 4 g of the hydroxymethyl urea solution prepared in step (1), mixing them under an ice bath for 30 min, warming the resultant mixture to 55 C. and then reacting the same under an atmosphere of nitrogen for 4 h to obtain a viscous product; and
(97) (3) granulating the obtained viscous product and oven drying the same to obtain a crop straw-based water-absorbing and water-retaining multi-nutrient biodegradable polymeric slow/controlled release fertilizer having a semi-interpenetrating network structure.
(98) In the resulting crop straw-based water-absorbing and water-retaining multi-nutrient biodegradable polymeric slow/controlled release fertilizer having a semi-interpenetrating network structure, the content of nitrogen is 16.83%, the content of phosphorus is 1.50% in terms of P.sub.2O.sub.5, the content of potassium is 19.49% in terms of K.sub.2O; and the water absorbency in tap water is 118 g/g.
Example 15
(99) A method for preparing a cellulose-based water-absorbing and water-retaining multi-nutrient biodegradable polymeric slow/controlled release fertilizer having a semi-interpenetrating network structure, comprising the steps of:
(100) (1) adding 4.06 g of formaldehyde and 6 g of urea respectively into a first reactor, adjusting the resultant system to pH=8 with a 5% KOH solution, and reacting the same at 40 C. for 2 h to obtain a hydroxymethyl urea solution;
(101) (2) adding 5 g of acrylic acid, 2 g of acrylamide and 0.7 g of carboxymethyl cellulose powder into a second reactor, and adding a 20 mass % KOH solution to adjust the neutralization degree of acrylic acid to 80%; and then adding 0.5 g of monopotassium phosphate, 0.021 g of ammonium persulfate and 12 g of the hydroxymethyl urea solution prepared in step (1), mixing them under an ice bath for 30 min, warming the resultant mixture to 55 C. and then reacting the same under an atmosphere of nitrogen for 4 h to obtain a viscous product; and
(102) (3) granulating the obtained viscous product and oven drying the same to obtain a cellulose-based water-absorbing and water-retaining multi-nutrient biodegradable polymeric slow/controlled release fertilizer having a semi-interpenetrating network structure.
(103) In the resulting cellulose-based water-absorbing and water-retaining multi-nutrient biodegradable polymeric slow/controlled release fertilizer having a semi-interpenetrating network structure, the content of nitrogen is 32.47%, the content of phosphorus is 0.96% in terms of P.sub.2O.sub.5, the content of potassium is 13.67% in terms of K.sub.2O; and the water absorbency in tap water is 46 g/g.
Example 16
(104) A method for preparing a cellulose-based water-absorbing and water-retaining multi-nutrient biodegradable polymeric slow/controlled release fertilizer having a semi-interpenetrating network structure, comprising the steps of:
(105) (1) adding 4.06 g of formaldehyde and 6 g of urea respectively into a first reactor, adjusting the resultant system to pH=8 with a 5% KOH solution, and reacting the same at 40 C. for 2 h to obtain a hydroxymethyl urea solution;
(106) (2) adding 5 g of acrylic acid, 2 g of acrylamide and 0.7 g of hydroxyethyl cellulose powder into a second reactor, and adding a 20 mass % KOH solution to adjust the neutralization degree of acrylic acid to 80%; and then adding 0.5 g of monopotassium phosphate, 0.021 g of ammonium persulfate and 12 g of the hydroxymethyl urea solution prepared in step (1), mixing them under an ice bath for 30 min, warming the resultant mixture to 55 C. and then reacting the same under an atmosphere of nitrogen for 4 h to obtain a viscous product; and
(107) (3) granulating the obtained viscous product and oven drying the same to obtain a cellulose-based water-absorbing and water-retaining multi-nutrient biodegradable polymeric slow/controlled release fertilizer having a semi-interpenetrating network structure.
(108) In the resulting cellulose-based water-absorbing and water-retaining multi-nutrient biodegradable polymeric slow/controlled release fertilizer having a semi-interpenetrating network structure, the content of nitrogen is 31.96%, the content of phosphorus is 0.94% in terms of P.sub.2O.sub.5, the content of potassium is 13.47% in terms of K.sub.2O; and the water absorbency in tap water is 62 g/g.
Example 17
(109) A method for preparing a cellulose-based water-absorbing and water-retaining multi-nutrient biodegradable polymeric slow/controlled release fertilizer having a semi-interpenetrating network structure, comprising the steps of:
(110) (1) adding 4.06 g of formaldehyde and 6 g of urea respectively into a first reactor, adjusting the resultant system to pH=8 with a 5% KOH solution, and reacting the same at 40 C. for 2 h to obtain a hydroxymethyl urea solution;
(111) (2) adding 4.375 g of acrylic acid, 2.625 g of acrylamide and 0.7 g of hydroxyethyl cellulose powder into a second reactor, and adding a 20 mass % KOH solution to adjust the neutralization degree of acrylic acid to 80%; and then adding 0.5 g of monopotassium phosphate, 0.021 g of ammonium persulfate and 12 g of the hydroxymethyl urea solution prepared in step (1), mixing them under an ice bath for 30 min, warming the resultant mixture to 55 C. and then reacting the same under an atmosphere of nitrogen for 4 h to obtain a viscous product; and
(112) (3) granulating the obtained viscous product and oven drying the same to obtain a cellulose-based water-absorbing and water-retaining multi-nutrient biodegradable polymeric slow/controlled release fertilizer having a semi-interpenetrating network structure.
(113) In the resulting cellulose-based water-absorbing and water-retaining multi-nutrient biodegradable polymeric slow/controlled release fertilizer having a semi-interpenetrating network structure, the content of nitrogen is 34.68%, the content of phosphorus is 0.89% in terms of P.sub.2O.sub.5, the content of potassium is 13.64% in terms of K.sub.2O; and the water absorbency in tap water is 71 g/g.
Example 18
(114) A method for preparing a cellulose-based water-absorbing and water-retaining multi-nutrient biodegradable polymeric slow/controlled release fertilizer having a semi-interpenetrating network structure, comprising the steps of:
(115) (1) adding 4.06 g of formaldehyde and 6 g of urea respectively into a first reactor, adjusting the resultant system to pH=8 with a 5% KOH solution, and reacting the same at 40 C. for 2 h to obtain a hydroxymethyl urea solution;
(116) (2) adding 4.375 g of acrylic acid, 2.625 g of acrylamide and 0.7 g of carboxymethyl cellulose powder into a second reactor, and adding a 20 mass % KOH solution to adjust the neutralization degree of acrylic acid to 80%; and then adding 0.5 g of monopotassium phosphate, 0.021 g of ammonium persulfate and 12 g of the hydroxymethyl urea solution prepared in step (1), mixing them under an ice bath for 30 min, warming the resultant mixture to 55 C. and then reacting the same under an atmosphere of nitrogen for 4 h to obtain a viscous product; and
(117) (3) granulating the obtained viscous product and oven drying the same to obtain a cellulose-based water-absorbing and water-retaining multi-nutrient biodegradable polymeric slow/controlled release fertilizer having a semi-interpenetrating network structure.
(118) In the resulting cellulose-based water-absorbing and water-retaining multi-nutrient biodegradable polymeric slow/controlled release fertilizer having a semi-interpenetrating network structure, the content of nitrogen is 33.84%, the content of phosphorus is 0.85% in terms of P.sub.2O.sub.5, the content of potassium is 12.86% in terms of K.sub.2O; and the water absorbency in tap water is 56 g/g.
Example 19
(119) A method for preparing a cellulose-based water-absorbing and water-retaining multi-nutrient biodegradable polymeric slow/controlled release fertilizer having a semi-interpenetrating network structure, comprising the steps of:
(120) (1) adding 4.06 g of formaldehyde and 6 g of urea respectively into a first reactor, adjusting the resultant system to pH=8 with a 5% KOH solution, and reacting the same at 40 C. for 2 h to obtain a hydroxymethyl urea solution;
(121) (2) adding 4.375 g of acrylic acid, 2.625 g of acrylamide and 0.7 g of hydroxyethyl cellulose powder into a second reactor, and adding a 20 mass % KOH solution to adjust the neutralization degree of acrylic acid to 80%; and then adding 1 g of monopotassium phosphate, 0.021 g of ammonium persulfate and 12 g of the hydroxymethyl urea solution prepared in step (1), mixing them under an ice bath for 30 min, warming the resultant mixture to 55 C. and then reacting the same under an atmosphere of nitrogen for 4 h to obtain a viscous product; and
(122) (3) granulating the obtained viscous product and oven drying the same to obtain a cellulose-based water-absorbing and water-retaining multi-nutrient biodegradable polymeric slow/controlled release fertilizer having a semi-interpenetrating network structure.
(123) In the resulting cellulose-based water-absorbing and water-retaining multi-nutrient biodegradable polymeric slow/controlled release fertilizer having a semi-interpenetrating network structure, the content of nitrogen is 30.65%, the content of phosphorus is 1.83% in terms of P.sub.2O.sub.5, the content of potassium is 18.47% in terms of K.sub.2O; and the water absorbency in tap water is 35 g/g.
Example 20
(124) A method for preparing a cellulose-based water-absorbing and water-retaining multi-nutrient biodegradable polymeric slow/controlled release fertilizer having a semi-interpenetrating network structure, comprising the steps of:
(125) (1) adding 4.06 g of formaldehyde and 6 g of urea respectively into a first reactor, adjusting the resultant system to pH=8 with a 5% KOH solution, and reacting the same at 40 C. for 2 h to obtain a hydroxymethyl urea solution;
(126) (2) adding 5 g of acrylic acid, 2 g of acrylamide and 0.35 g of hydroxyethyl cellulose powder into a second reactor, and adding a 20 mass % KOH solution to adjust the neutralization degree of acrylic acid to 80%; and then adding 0.5 g of monopotassium phosphate, 0.021 g of ammonium persulfate and 12 g of the hydroxymethyl urea solution prepared in step (1), mixing them under an ice bath for 30 min, warming the resultant mixture to 55 C. and then reacting the same under an atmosphere of nitrogen for 4 h to obtain a viscous product; and
(127) (3) granulating the obtained viscous product and oven drying the same to obtain a cellulose-based water-absorbing and water-retaining multi-nutrient biodegradable polymeric slow/controlled release fertilizer having a semi-interpenetrating network structure.
(128) In the resulting cellulose-based water-absorbing and water-retaining multi-nutrient biodegradable polymeric slow/controlled release fertilizer having a semi-interpenetrating network structure, the content of nitrogen is 35.31%, the content of phosphorus is 1.08% in terms of P.sub.2O.sub.5, the content of potassium is 14.67% in terms of K.sub.2O; and the water absorbency in tap water is 54 g/g.
Example 21
(129) A method for preparing a cellulose-based water-absorbing and water-retaining multi-nutrient biodegradable polymeric slow/controlled release fertilizer having a semi-interpenetrating network structure, comprising the steps of:
(130) (1) adding 2.03 g of formaldehyde and 3 g of urea respectively into a first reactor, adjusting the resultant system to pH=8 with a 5% KOH solution, and reacting the same at 40 C. for 2 h to obtain a hydroxymethyl urea solution;
(131) (2) adding 4.375 g of acrylic acid, 2.625 g of acrylamide and 0.7 g of hydroxyethyl cellulose powder into a second reactor, and adding a 20 mass % KOH solution to adjust the neutralization degree of acrylic acid to 80%; and then adding 0.5 g of monopotassium phosphate, 0.021 g of ammonium persulfate and 6 g of the hydroxymethyl urea solution prepared in step (1), mixing them under an ice bath for 30 min, warming the resultant mixture to 55 C. and then reacting the same under an atmosphere of nitrogen for 4 h to obtain a viscous product; and
(132) (3) granulating the obtained viscous product and oven drying the same to obtain a cellulose-based water-absorbing and water-retaining multi-nutrient biodegradable polymeric slow/controlled release fertilizer having a semi-interpenetrating network structure.
(133) In the resulting cellulose-based water-absorbing and water-retaining multi-nutrient biodegradable polymeric slow/controlled release fertilizer having a semi-interpenetrating network structure, the content of nitrogen is 24.73%, the content of phosphorus is 1.95% in terms of P.sub.2O.sub.5, the content of potassium is 15.82% in terms of K.sub.2O; and the water absorbency in tap water is 134 g/g.
(134) While illustrative embodiments have been illustrated and described, it will be appreciated that various changes can be made therein without departing from the spirit and scope of the invention.