CN113527014A - Nitration inhibitor and preparation method thereof - Google Patents
Nitration inhibitor and preparation method thereof Download PDFInfo
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- CN113527014A CN113527014A CN202110993327.3A CN202110993327A CN113527014A CN 113527014 A CN113527014 A CN 113527014A CN 202110993327 A CN202110993327 A CN 202110993327A CN 113527014 A CN113527014 A CN 113527014A
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- nitrification inhibitor
- grinding disc
- granulating
- box body
- catalyst
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- 239000003112 inhibitor Substances 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000006396 nitration reaction Methods 0.000 title claims description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 44
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000003223 protective agent Substances 0.000 claims abstract description 34
- 239000000618 nitrogen fertilizer Substances 0.000 claims abstract description 30
- 239000007788 liquid Substances 0.000 claims abstract description 27
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 22
- 230000000802 nitrating effect Effects 0.000 claims abstract description 22
- 239000000084 colloidal system Substances 0.000 claims abstract description 21
- 230000001681 protective effect Effects 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 11
- 238000000227 grinding Methods 0.000 claims description 48
- 239000000463 material Substances 0.000 claims description 31
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 26
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 13
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 13
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 13
- 239000000920 calcium hydroxide Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 230000000694 effects Effects 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 10
- 108010010803 Gelatin Proteins 0.000 claims description 9
- ULGYAEQHFNJYML-UHFFFAOYSA-N [AlH3].[Ca] Chemical compound [AlH3].[Ca] ULGYAEQHFNJYML-UHFFFAOYSA-N 0.000 claims description 9
- 235000010489 acacia gum Nutrition 0.000 claims description 9
- 239000008273 gelatin Substances 0.000 claims description 9
- 229920000159 gelatin Polymers 0.000 claims description 9
- 235000019322 gelatine Nutrition 0.000 claims description 9
- 235000011852 gelatine desserts Nutrition 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- 229920000084 Gum arabic Polymers 0.000 claims description 7
- 241000978776 Senegalia senegal Species 0.000 claims description 7
- 239000000205 acacia gum Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 6
- 229910052791 calcium Inorganic materials 0.000 claims description 6
- 239000011575 calcium Substances 0.000 claims description 6
- 239000000499 gel Substances 0.000 claims description 6
- 238000010521 absorption reaction Methods 0.000 claims description 4
- 230000009471 action Effects 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims description 3
- 239000012295 chemical reaction liquid Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000005516 engineering process Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 230000005764 inhibitory process Effects 0.000 claims description 3
- 238000000622 liquid--liquid extraction Methods 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 238000000638 solvent extraction Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- 239000001785 acacia senegal l. willd gum Substances 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- 238000004064 recycling Methods 0.000 claims description 2
- 239000002689 soil Substances 0.000 abstract description 12
- MMDJDBSEMBIJBB-UHFFFAOYSA-N [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] Chemical compound [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] MMDJDBSEMBIJBB-UHFFFAOYSA-N 0.000 abstract description 10
- 239000003337 fertilizer Substances 0.000 abstract description 9
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 abstract description 5
- 239000002699 waste material Substances 0.000 abstract description 5
- 230000006872 improvement Effects 0.000 abstract description 2
- 238000005469 granulation Methods 0.000 description 16
- 230000003179 granulation Effects 0.000 description 16
- 238000005453 pelletization Methods 0.000 description 16
- 238000001125 extrusion Methods 0.000 description 11
- 239000008187 granular material Substances 0.000 description 10
- 239000013078 crystal Substances 0.000 description 5
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000003912 environmental pollution Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000001546 nitrifying effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- LXKCHCXZBPLTAE-UHFFFAOYSA-N 3,4-dimethyl-1H-pyrazole phosphate Chemical compound OP(O)(O)=O.CC1=CNN=C1C LXKCHCXZBPLTAE-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 239000003124 biologic agent Substances 0.000 description 1
- 239000013590 bulk material Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- DCUJJWWUNKIJPH-UHFFFAOYSA-N nitrapyrin Chemical compound ClC1=CC=CC(C(Cl)(Cl)Cl)=N1 DCUJJWWUNKIJPH-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
- C05G3/90—Mixtures of one or more fertilisers with additives not having a specially fertilising activity for affecting the nitrification of ammonium compounds or urea in the soil
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P60/00—Technologies relating to agriculture, livestock or agroalimentary industries
- Y02P60/20—Reduction of greenhouse gas [GHG] emissions in agriculture, e.g. CO2
- Y02P60/21—Dinitrogen oxide [N2O], e.g. using aquaponics, hydroponics or efficiency measures
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Soil Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Fertilizers (AREA)
Abstract
The invention discloses a nitrification inhibitor and a preparation method thereof, and relates to the technical field of soil improvement. The nitrification inhibitor comprises the following components: p-dichlorobenzene, a nitrating agent, a catalyst protective agent and a protective colloid; the nitrating agent is mixed acid consisting of nitric acid and sulfuric acid. The preparation method of the nitrification inhibitor comprises the following steps: adding a nitrating agent, p-dichlorobenzene, a catalyst protective agent and a protective colloid into a tubular reactor to obtain a reaction solution; the liquid nitrification inhibitor is added into the nitrogen fertilizer to be processed into the fertilizer. The invention has the advantages that: the product of the nitrification inhibitor has high total yield and good stability; the method can effectively avoid the volatilization loss of the nitrification inhibitor, avoid the generation of a large amount of waste acid, can be recycled, can save energy, can well inhibit the conversion of ammonium nitrogen in the nitrogen fertilizer into nitrate nitrogen by adding the nitrification inhibitor, and has high utilization rate of the fertilizer.
Description
Technical Field
The invention relates to the technical field of soil improvement, and particularly relates to a nitrification inhibitor and a preparation method thereof.
Background
After being applied to soil, chemical nitrogen fertilizers are easy to run off along with water in the form of nitrate nitrogen, which is one of the main reasons for low utilization rate of the fertilizers. The method has the advantages that the water eutrophication can be caused by the over-high content of nitrate nitrogen, the harm can be caused to livestock and human beings in serious cases, the ammonium nitrogen is delayed to be oxidized into the nitrate nitrogen by microorganisms in the soil, the method is an effective way for reducing the leaching of the nitrate nitrogen, and the most used method at present is to utilize a nitrification inhibitor to inhibit the occurrence of the nitrification of the nitrogen fertilizer.
Nitrification inhibitors such as 3, 4-dimethylpyrazole phosphate (DMPP), 2-chloro-6 (trichloromethyl) pyridine, dicyandiamide (DCD) and the like are chemical or natural biological agents which are developed by adding the nitrification inhibitors into a nitrogen fertilizer through a certain process so as to reduce the pollution to the environment and improve the utilization rate of the fertilizer and inhibit the conversion of ammonium nitrogen into nitrate nitrogen. It has certain toxicity to nitrifying bacteria and can inhibit the activity of some nitrifying bacteria so as to inhibit the intensity of nitrification.
However, the nitrification inhibitors DMPP, DCD, etc. widely studied and applied at home and abroad at present have certain defects, the effect of the nitrification inhibitors DMPP, DCD, etc. when in use is greatly affected by the environment (degradation rate of the nitrification inhibitors, soil temperature and humidity, etc.), especially in southern areas of China, most nitrification inhibitors are easy to be leached and deliquesced due to humid environment, the ability of inhibiting nitrification is greatly reduced, and one problem associated with the use of the nitrification inhibitors is their high volatility, which causes continuous loss of active components, in addition, some nitrification inhibitors can use concentrated sulfuric acid as a catalyst during processing, although the conversion rate is high when the concentrated sulfuric acid is used in a large amount, which can exceed 99%, the use of sulfuric acid in a large amount can generate a large amount of waste acid, which is difficult to be regenerated and used, and the direct discharge causes serious environmental pollution, the treatment is troublesome, and the nitrification inhibitors can be made into crystals, when the liquid nitrification inhibitor is generated, nitrification inhibitor crystals need to be formed through a series of operations, and when the nitrification inhibitor crystals are added into the liquid fertilizer, the nitrification inhibitor crystals need to be reheated into a liquid state, so that much energy is consumed.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a nitrification inhibitor and a preparation method thereof, which can solve the problems that the effect of the nitrification inhibitor in the prior art is greatly influenced by the environment when in use, most nitrification inhibitors are easy to elute and deliquesce, the capability of inhibiting nitrification is greatly reduced, the nitrification inhibitor has high volatility to cause continuous loss of active components when in use, concentrated sulfuric acid can generate a large amount of waste acid which is difficult to be recycled as a catalyst, the waste acid is directly discharged to cause serious environmental pollution, and the energy consumption is high when in use.
In order to solve the technical problems, the technical scheme of the invention is as follows: a nitrification inhibitor comprises the following components: 10-15 parts of p-dichlorobenzene, 15-25 parts of nitrating agent, 2-5 parts of catalyst protective agent and 60-70 parts of protective colloid;
the p-dichlorobenzene is liquid p-dichlorobenzene with the content of more than 99.5 percent;
the nitrating agent is mixed acid consisting of 98% nitric acid and 85-90% sulfuric acid, and the mass ratio of the nitric acid to the sulfuric acid is 1.5: 1;
the catalyst protective agent is sulfate radical type calcium-aluminum double hydroxide.
Further, the protective colloid is one of or the combination of the arabic gum powder and the gelatin;
the catalyst protective agent is synthesized by using raw materials of calcium hydroxide, calcium sulfate and aluminum hydroxide.
Further, when the protective colloid is the combination of the gum arabic powder and the gelatin, the mass ratio of the gum arabic powder to the gelatin is 1: 1.6; in the catalyst protective agent, the mass ratio of calcium hydroxide, calcium sulfate and aluminum hydroxide is 1:1: 1.8.
A method for preparing a nitrification inhibitor is characterized in that: the method comprises the following steps:
s1, adding a nitrating agent into the tubular reactor according to the proportion;
s2, adding liquid p-dichlorobenzene, a catalyst protective agent and a protective colloid into the tubular reactor, taking the p-dichlorobenzene and nitric acid in a nitrating agent as raw materials, carrying out continuous reaction in the tubular reactor under the catalytic action of a concentrated sulfuric acid catalyst in the nitrating agent, the water absorption action of the catalyst protective agent and the protection of the protective colloid, and carrying out nitration reaction for 15-50min by adopting a tubular reaction technology at the temperature of 100-200 ℃ to obtain a reaction liquid;
s3, carrying out liquid-liquid extraction on the solution to prepare the liquid nitrification inhibitor.
Further, the preparation method of the catalyst protective agent comprises the following steps:
s1, mixing calcium hydroxide, calcium sulfate and aluminum hydroxide in a certain proportion into a reactor, and adding water higher than the materials for mixing;
s2, synthesizing calcium sulphoaluminate gel in the reactor, then crystallizing the calcium sulphoaluminate gel for 12-16h at 90-150 ℃, cooling to 30-50 ℃, stirring for 12-16h, then heating to 90-150 ℃, and circulating for 3-5 times to obtain the sulfate radical type catalyst protective agent of the calcium-aluminum double hydroxide.
Further, the liquid nitrification inhibitor is added into the liquid nitrogen fertilizer to be fully mixed, cooled to be solid after being mixed, and processed into the nitrogen fertilizer with nitrification inhibition effect through a nitrogen fertilizer granulation device.
Furthermore, the nitrogen fertilizer granulating device comprises a granulating box body and a feeding bin, wherein the feeding bin is positioned at the top of the granulating box body, the bottom of the feeding bin is communicated with the inside of the granulating box body through a feeding channel, a rotating grinding disc is arranged above the granulating box body, a fixed grinding disc is arranged below the rotating grinding disc, and a gap is formed between the fixed grinding disc and the rotating grinding disc;
a plurality of blanking holes are formed in the fixed grinding disc and are through holes;
a granulating plate is arranged below the fixed grinding disc, a plurality of granulating holes are formed in the granulating plate, the plurality of granulating holes have different diameters, and a plurality of extruding rollers are arranged above the granulating plate;
a plurality of layers of obliquely arranged collecting sieves are arranged below the granulating plate, the sieve pores of the collecting sieves positioned above are larger than those of the collecting sieves positioned below, the lower ends of the plurality of layers of collecting sieves extend out of the granulating box body respectively, and collecting boxes are connected below the lower ends of the plurality of layers of collecting sieves respectively;
and a recycling box is arranged at the bottom of the granulating box body.
Furthermore, the fixed grinding disc is fixedly arranged in the granulating box body, and the center of the bottom of the rotating grinding disc is supported in a groove at the center of the fixed grinding disc through a rotating shaft;
a driving motor is arranged outside the granulating box body, a gear is arranged on an output shaft of the driving motor, meshing teeth are arranged on the periphery of the rotary grinding disc, the gear is meshed with the meshing teeth, the driving motor drives the gear to rotate to drive the rotary grinding disc to rotate, and the side of the gear extends into the granulating box body;
the top center of the rotary grinding disc is provided with a feeding hole, and the feeding hole is communicated with the bottom of the feeding channel.
Furthermore, the bottom of the rotary grinding disc is provided with a plurality of discharge holes, the discharge holes are uniformly distributed by taking the rotating shaft as the center, and the feeding holes are respectively communicated with the plurality of discharge holes.
Further, the diameter of the blanking hole is larger than that of the granulating hole.
The invention has the advantages that: liquid p-dichlorobenzene and nitric acid are used as raw materials, concentrated sulfuric acid is used as a catalyst for catalysis, a tubular reaction device is used for replacing a kettle type reaction device for nitration reaction, the operation is simple and easy to control, the method is suitable for industrial mass production, and the total yield of nitration inhibitor products is high;
the catalyst protective agent is added in the reaction, the catalyst protective agent is sulfate radical type calcium-aluminum binary hydroxide, and the catalyst protective agent has a larger specific surface area of 30-36 square meters per gram and strong water absorption performance, so that the problem that concentrated sulfuric acid generates a large amount of waste acid as a catalyst is solved, and the catalyst protective agent can be recycled after being calcined at the temperature of 800-1000 ℃, so that the environmental pollution is prevented;
the prepared nitrification inhibitor has good stability, reduces the degree of the nitrification inhibitor influenced by the environment when in use, improves the application effect of the nitrification inhibitor, and can well inhibit the conversion of ammonium nitrogen in a nitrogen fertilizer to nitrate nitrogen;
the nitrification inhibitor generated by the reaction is in a liquid state, the nitrification inhibitor is used as the liquid state and is mixed with the liquid nitrogen fertilizer, so that the mixing is more complete, the nitrification inhibitor is not prepared into crystals and is converted into the liquid state, and the energy consumption can be saved;
can carry out the manufacturing of granule with nitrogen fertilizer mixture through nitrogen fertilizer prilling granulator, the extrusion granulation is effectual, and the granulation is efficient, and can extrude the extrusion and make the granular fertilizer of different diameters size, and the nitrogen fertilizer that has the nitrification inhibitor who produces is difficult for following water loss with the form of nitrate nitrogen after applying into soil, and the fertilizer high-usage.
Drawings
FIG. 1 is a schematic structural view of a nitrogen fertilizer granulating apparatus of the present invention;
figure 2 is a bottom structure schematic diagram of a rotating grinding disc of the nitrogen fertilizer granulation device of the invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to specific embodiments. The following examples are presented to enable one of ordinary skill in the art to more fully understand the present invention and are not intended to limit the scope of the embodiments described herein.
Example 1:
a nitrification inhibitor comprises the following components: 10 parts of p-dichlorobenzene, 15 parts of nitrating agent, 5 parts of catalyst protective agent and 70 parts of protective colloid.
The paradichlorobenzene is liquid paradichlorobenzene with the content of more than 99.5 percent, the nitrating agent is mixed acid consisting of 98 percent nitric acid and 85 percent sulfuric acid, the mass ratio of the nitric acid to the sulfuric acid is 1.5:1, and the protective colloid is gum arabic powder.
The catalyst protective agent is sulfate radical type calcium-aluminum binary hydroxide, and is synthesized by using raw materials of calcium hydroxide, calcium sulfate and aluminum hydroxide, wherein the mass ratio of the calcium hydroxide to the calcium sulfate to the aluminum hydroxide is 1:1: 1.8.
A preparation method of a nitrification inhibitor comprises the following steps:
s1, adding a nitrating agent into the tubular reactor according to the proportion;
s2, adding liquid p-dichlorobenzene, a catalyst protective agent and a protective colloid into the tubular reactor, taking the p-dichlorobenzene and nitric acid in a nitrating agent as raw materials, carrying out continuous reaction in the tubular reactor under the catalytic action of a concentrated sulfuric acid catalyst in the nitrating agent, the water absorption action of the catalyst protective agent and the protection of the protective colloid, and carrying out nitration reaction for 15-50min by adopting a tubular reaction technology at the temperature of 100-200 ℃ to obtain a reaction liquid;
s3, carrying out liquid-liquid extraction on the solution to prepare the liquid nitrification inhibitor.
The preparation method of the catalyst protective agent comprises the following steps:
s1, mixing calcium hydroxide, calcium sulfate and aluminum hydroxide in a certain proportion into a reactor, and adding water higher than the materials for mixing;
s2, synthesizing calcium sulphoaluminate gel in the reactor, then crystallizing the calcium sulphoaluminate gel for 12-16h at 90-150 ℃, cooling to 30-50 ℃, stirring for 12-16h, then heating to 90-150 ℃, and circulating for 3-5 times to obtain the sulfate radical type catalyst protective agent of the calcium-aluminum double hydroxide.
Example 2:
15 parts of p-dichlorobenzene, 17 parts of nitrating agent, 3 parts of catalyst protective agent and 65 parts of protective colloid.
The p-dichlorobenzene is liquid p-dichlorobenzene with the content of more than 99.5 percent, the nitrating agent is mixed acid consisting of 98 percent nitric acid and 90 percent sulfuric acid, the mass ratio of the nitric acid to the sulfuric acid is 1.5:1, and the protective colloid is gelatin.
The catalyst protective agent is sulfate radical type calcium-aluminum binary hydroxide, and is synthesized by using raw materials of calcium hydroxide, calcium sulfate and aluminum hydroxide, wherein the mass ratio of the calcium hydroxide to the calcium sulfate to the aluminum hydroxide is 1:1: 1.8.
The specific preparation method of the nitrification inhibitor and the catalyst protectant are the same as those in example 1.
Example 3:
13 parts of p-dichlorobenzene, 22 parts of nitrating agent, 5 parts of catalyst protective agent and 60 parts of protective colloid.
The p-dichlorobenzene is liquid p-dichlorobenzene with the content of more than 99.5 percent, the nitrating agent is mixed acid consisting of 98 percent nitric acid and 87 percent sulfuric acid, and the mass ratio of the nitric acid to the sulfuric acid is 1.5: 1; the protective colloid is the combination of gum arabic powder and gelatin, and the mass ratio of the gum arabic powder to the gelatin is 1: 1.6.
The catalyst protective agent is sulfate radical type calcium-aluminum binary hydroxide, and is synthesized by using raw materials of calcium hydroxide, calcium sulfate and aluminum hydroxide, wherein the mass ratio of the calcium hydroxide to the calcium sulfate to the aluminum hydroxide is 1:1: 1.8.
The specific preparation method of the nitrification inhibitor and the catalyst protectant are the same as those in example 1.
Liquid p-dichlorobenzene and nitric acid are used as raw materials, concentrated sulfuric acid is used as a catalyst for catalysis, a catalyst protective agent is used as a protective agent of the concentrated sulfuric acid catalyst, and a tubular reaction device is used for nitration reaction, so that the nitration inhibitor prepared in the examples 1-3 is high in overall yield, good in stability under the action of protective colloid, capable of effectively avoiding volatilization loss of the nitration inhibitor and capable of preventing continuous loss of active components.
The nitrification inhibitor prepared in the embodiment 1-3 is spread in the soil before the chemical nitrogen fertilizer is applied to the soil, when the nitrification inhibitor prepared in the embodiment 1 is applied, the minimum concentration of the applied soil is 0.5-10ppm, the effective time is 6 weeks, and the volatilization loss is reduced by 70 percent; when the nitrification inhibitor prepared in the example 2 is applied, the effective time is 9 weeks when the minimum concentration of the nitrification inhibitor applied to soil is 0.5-10ppm, and the volatilization loss is reduced by 85 percent; when the nitrification inhibitor prepared in example 3 is applied, when the minimum concentration applied to soil is 0.5-10ppm, the effective time is 7 weeks, the volatilization loss is reduced by 75%, the examples 1-3 well inhibit the conversion of ammonium nitrogen in the nitrogen fertilizer into nitrate nitrogen, the degree of environmental influence on the nitrification inhibitor during use is reduced, the application effect of the nitrification inhibitor is good, and example 2 is the best example.
Example 4: the liquid nitrification inhibitor prepared in the embodiment 1-3 is added into the liquid nitrogen fertilizer to be fully mixed, the mixture is cooled to be solid, the nitrogen fertilizer with nitrification inhibition effect is prepared by a nitrogen fertilizer granulation device, and the prepared nitrogen fertilizer with nitrification inhibitor is not easy to run off along with water in the form of nitrate nitrogen after being applied to soil.
The specific nitrogen fertilizer granulating device has the following structure:
as shown in figure 1, the nitrogen fertilizer granulating device comprises a granulating box body 1 and a feeding bin 2, wherein the feeding bin 2 is positioned in the middle of the top of the granulating box body 1, and the bottom of the feeding bin 2 is communicated with the inside of the granulating box body 1 through a feeding channel 3.
The top of pelletization box 1 is equipped with rotates mill 4, and the below of rotating mill 4 is equipped with fixed mill 5, is equipped with the space between fixed mill 5 and the rotation mill 4, and fixed mill 5 fixed mounting is inside pelletization box 1, and the bottom center of rotating mill 4 supports in the recess at fixed mill 5 center through pivot 6, is equipped with the bearing in the recess, and pivot 6 passes through the bearing installation, and rotation mill 4 supports through pivot 6.
The externally mounted of pelletization box 1 has driving motor 7, installs gear 8 on driving motor 7's the output shaft, and the periphery of rotating mill 4 is equipped with the meshing tooth, and gear 8 sets up with the meshing tooth meshing, and driving motor 7 drive gear 8 rotates and drives and rotate mill 4 and rotate, and the avris of gear 8 stretches into inside the pelletization box 1.
The center of the top of the rotary grinding disc 4 is provided with a feeding hole which is communicated with the bottom of the feeding channel 3, materials enter the feeding channel 3 through the feeding bin 2 and then enter the feeding hole on the rotary grinding disc 4, as shown in figure 2, the bottom of the rotary grinding disc 4 is provided with a plurality of discharge holes 41, in the embodiment, 6 discharge holes 41 are arranged, the discharge holes 41 are uniformly distributed by taking the rotating shaft 6 as the center, the feeding hole is respectively communicated with the 6 discharge holes 41 through an inclined channel, the materials enter the feeding hole and then enter the discharge holes 41 through the inclined channel, the rotary grinding disc 4 rotates by taking the rotating shaft 6 as the center, the feeding hole at the top of the rotary grinding disc 4 is always positioned at the bottom of the feeding channel 3, the materials can be continuously added and discharged to the bottom of the rotary grinding disc 4 through the discharge holes 41, the materials are added while the rotary grinding disc 4 is extruded, the processing process is smooth, the materials are directly spread and granulated, and the granulating efficiency is high, the material between the fixed grinding disc 5 and the rotating grinding disc 4 is primarily extruded through the relative rotation of the two.
Be equipped with a plurality of unloading holes 51 on the fixed mill 5, unloading hole 51 is the through-hole, the below of fixed mill 5 is equipped with pelletization board 9, material after the extrusion falls to the pelletization board 9 of below through unloading hole 51 on the fixed mill 5 on, be equipped with a plurality of pelletization holes 91 on the pelletization board 9, the diameter in unloading hole 51 is greater than the diameter in pelletization hole 91, a plurality of pelletization holes 91 have different diameters, can make the granule of different diameters simultaneously, the top of pelletization board 9 is equipped with several squeeze roll 10, extrude the granulation through the material of squeeze roll 10 extrusion on to pelletization board 9, twice extrusion of different modes makes the extrusion granulation effect of material better.
The squeeze roll 10 is installed on the granulation box body 1 through a bearing, and the rotating motor is installed on the outer side of the granulation box body 1, and the rotating motor drives the squeeze roll 10 to rotate to extrude and granulate the materials.
Several layers of collection sieve 11 that the slope set up are installed to the below of pelletization board 9, be equipped with two-layer collection sieve 11 in this embodiment, the sieve mesh that is located the collection sieve 11 of top is greater than the sieve mesh that is located the collection sieve 11 of below, the low side of two-layer collection sieve 11 stretches out the outside of pelletization box 1 respectively, and the side below of the low side of two-layer collection sieve 11 is connected with collecting box 12 respectively, the length of two-layer collection sieve 11 is different, make two collecting box 12 setting of staggering, the bottom of pelletization box 1 is equipped with collection box 13, the granule of extrusion granulation falls on the collection sieve 11 of below, filter the collection through the collection sieve 11 that has not equidimension sieve mesh, the granule of different specifications is collected to accessible collecting box 12, the bulk material that does not make the granule falls to retrieve in the collection box 13 of below.
The working principle is as follows: nitrogenous fertilizer solid materials added with nitrification inhibitor enter a material inlet channel 3 through a material inlet bin 2 and then enter a material inlet hole on a rotary grinding disc 4, and then enter a material outlet hole 41 through an inclined channel, the rotary grinding disc 4 rotates by taking a rotating shaft 6 as a center, the material inlet hole at the top of the rotary grinding disc 4 is always positioned at the bottom of the material inlet channel 3, the materials can be continuously added, the materials are discharged to the bottom of the rotary grinding disc 4 through the material outlet hole, the rotary grinding disc 4 carries out material addition while carrying out extrusion, the materials are directly paved for granulation, the granulation efficiency is high, the materials added between the fixed grinding disc 5 and the rotary grinding disc 4 are primarily extruded through the relative rotation of the fixed grinding disc 5 and the rotary grinding disc 4, the extruded materials fall onto a granulating plate 9 below through a material outlet hole 51 on the fixed grinding disc 5, the materials on the granulating plate 9 are extruded and granulated through an extruding roller 10, and the extrusion of the materials in two different modes can ensure that the extrusion granulation effect of the materials is better, and need not carry through extra drive arrangement, a plurality of pelletization holes 91 have different diameters, can make the granule of different diameters simultaneously, and the granule after the extrusion granulation falls on the collection sieve 11 of below, has the collection sieve 11 of equidimension sieve mesh through the multilayer and filters the collection, can collect the granule of different specifications, and does not make the scattered form material of granule and directly falls to retrieve in the collection box 13 of below and pelletize again, avoids extravagant.
The nitrogen fertilizer granulation device can be used for manufacturing the nitrogen fertilizer solid added with the nitrification inhibitor into particles, has high granulation efficiency, and can extrude and press the particles to manufacture the granular fertilizers with different diameters.
The foregoing shows and describes the general principles and features of the present invention, together with the advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. A nitrification inhibitor, characterized by: comprises the following components: 10-15 parts of p-dichlorobenzene, 15-25 parts of nitrating agent, 2-5 parts of catalyst protective agent and 60-70 parts of protective colloid;
the p-dichlorobenzene is liquid p-dichlorobenzene with the content of more than 99.5 percent;
the nitrating agent is mixed acid consisting of 98% nitric acid and 85-90% sulfuric acid, and the mass ratio of the nitric acid to the sulfuric acid is 1.5: 1;
the catalyst protective agent is sulfate radical type calcium-aluminum double hydroxide.
2. The nitrification inhibitor according to claim 1, wherein: the protective colloid is one or the combination of the arabic gum powder and the gelatin;
the catalyst protective agent is synthesized by using raw materials of calcium hydroxide, calcium sulfate and aluminum hydroxide.
3. A nitrification inhibitor according to claim 2, wherein: when the protective colloid is the combination of the gum arabic powder and the gelatin, the mass ratio of the gum arabic powder to the gelatin is 1: 1.6; in the catalyst protective agent, the mass ratio of calcium hydroxide, calcium sulfate and aluminum hydroxide is 1:1: 1.8.
4. A process for the preparation of the nitrification inhibitor of claim 1, wherein: the method comprises the following steps:
s1, adding a nitrating agent into the tubular reactor according to the proportion;
s2, adding liquid p-dichlorobenzene, a catalyst protective agent and a protective colloid into the tubular reactor, taking the p-dichlorobenzene and nitric acid in a nitrating agent as raw materials, carrying out continuous reaction in the tubular reactor under the catalytic action of a concentrated sulfuric acid catalyst in the nitrating agent, the water absorption action of the catalyst protective agent and the protection of the protective colloid, and carrying out nitration reaction for 15-50min by adopting a tubular reaction technology at the temperature of 100-200 ℃ to obtain a reaction liquid;
s3, carrying out liquid-liquid extraction on the solution to prepare the liquid nitrification inhibitor.
5. A nitrification inhibitor according to claim 2, wherein: the preparation method of the catalyst protective agent comprises the following steps:
s1, mixing calcium hydroxide, calcium sulfate and aluminum hydroxide in a certain proportion into a reactor, and adding water higher than the materials for mixing;
s2, synthesizing calcium sulphoaluminate gel in the reactor, then crystallizing the calcium sulphoaluminate gel for 12-16h at 90-150 ℃, cooling to 30-50 ℃, stirring for 12-16h, then heating to 90-150 ℃, and circulating for 3-5 times to obtain the sulfate radical type catalyst protective agent of the calcium-aluminum double hydroxide.
6. The nitrification inhibitor according to claim 1, wherein: the liquid nitrification inhibitor is directly added into the liquid nitrogen fertilizer to be fully mixed, cooled into solid after being mixed, and processed into the nitrogen fertilizer with nitrification inhibition effect through a nitrogen fertilizer granulating device.
7. The nitrification inhibitor according to claim 6, wherein: the nitrogen fertilizer granulating device comprises a granulating box body and a feeding bin, wherein the feeding bin is positioned at the top of the granulating box body, the bottom of the feeding bin is communicated with the inside of the granulating box body through a feeding channel, a rotating grinding disc is arranged above the granulating box body, a fixed grinding disc is arranged below the rotating grinding disc, and a gap is formed between the fixed grinding disc and the rotating grinding disc;
a plurality of blanking holes are formed in the fixed grinding disc and are through holes;
a granulating plate is arranged below the fixed grinding disc, a plurality of granulating holes are formed in the granulating plate, the plurality of granulating holes have different diameters, and a plurality of extruding rollers are arranged above the granulating plate;
a plurality of layers of obliquely arranged collecting sieves are arranged below the granulating plate, the sieve pores of the collecting sieves positioned above are larger than those of the collecting sieves positioned below, the lower ends of the plurality of layers of collecting sieves extend out of the granulating box body respectively, and collecting boxes are connected below the lower ends of the plurality of layers of collecting sieves respectively;
and a recycling box is arranged at the bottom of the granulating box body.
8. The nitrification inhibitor according to claim 7, wherein: the fixed grinding disc is fixedly arranged in the granulating box body, and the center of the bottom of the rotating grinding disc is supported in a groove in the center of the fixed grinding disc through a rotating shaft;
a driving motor is arranged outside the granulating box body, a gear is arranged on an output shaft of the driving motor, meshing teeth are arranged on the periphery of the rotary grinding disc, the gear is meshed with the meshing teeth, the driving motor drives the gear to rotate to drive the rotary grinding disc to rotate, and the side of the gear extends into the granulating box body;
the top center of the rotary grinding disc is provided with a feeding hole, and the feeding hole is communicated with the bottom of the feeding channel.
9. The nitrification inhibitor according to claim 8, wherein: the bottom of the rotary grinding disc is provided with a plurality of discharge holes, the discharge holes are uniformly distributed by taking the rotating shaft as the center, and the feed holes are respectively communicated with the plurality of discharge holes.
10. The nitrification inhibitor according to claim 7, wherein: the diameter of the blanking hole is larger than that of the granulating hole.
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