CN111440035A - Manufacturing equipment and manufacturing method of humic acid chelated rare earth water-soluble fertilizer - Google Patents
Manufacturing equipment and manufacturing method of humic acid chelated rare earth water-soluble fertilizer Download PDFInfo
- Publication number
- CN111440035A CN111440035A CN202010371182.9A CN202010371182A CN111440035A CN 111440035 A CN111440035 A CN 111440035A CN 202010371182 A CN202010371182 A CN 202010371182A CN 111440035 A CN111440035 A CN 111440035A
- Authority
- CN
- China
- Prior art keywords
- humic acid
- rare earth
- fertilizer
- manufacturing
- reaction device
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000004021 humic acid Substances 0.000 title claims abstract description 93
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 84
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 239000003337 fertilizer Substances 0.000 title claims abstract description 61
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 46
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 44
- 238000006243 chemical reaction Methods 0.000 claims abstract description 73
- 230000009920 chelation Effects 0.000 claims abstract description 38
- -1 rare earth compound Chemical class 0.000 claims abstract description 24
- 239000011573 trace mineral Substances 0.000 claims abstract description 22
- 235000013619 trace mineral Nutrition 0.000 claims abstract description 22
- 238000006277 sulfonation reaction Methods 0.000 claims abstract description 21
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 238000004806 packaging method and process Methods 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 8
- 150000003385 sodium Chemical class 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- 239000003245 coal Substances 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- BYMHXIQVEAYSJD-UHFFFAOYSA-M sodium;4-sulfophenolate Chemical compound [Na+].OC1=CC=C(S([O-])(=O)=O)C=C1 BYMHXIQVEAYSJD-UHFFFAOYSA-M 0.000 claims description 5
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 5
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 5
- 229960001763 zinc sulfate Drugs 0.000 claims description 5
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000011790 ferrous sulphate Substances 0.000 claims description 4
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 4
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 4
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 4
- 229940099596 manganese sulfate Drugs 0.000 claims description 4
- 239000011702 manganese sulphate Substances 0.000 claims description 4
- 235000007079 manganese sulphate Nutrition 0.000 claims description 4
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 4
- VQTGUFBGYOIUFS-UHFFFAOYSA-N nitrosylsulfuric acid Chemical compound OS(=O)(=O)ON=O VQTGUFBGYOIUFS-UHFFFAOYSA-N 0.000 claims description 4
- 238000012805 post-processing Methods 0.000 claims description 4
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 claims description 3
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 claims description 3
- 239000011609 ammonium molybdate Substances 0.000 claims description 3
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 3
- 229940010552 ammonium molybdate Drugs 0.000 claims description 3
- 229910021538 borax Inorganic materials 0.000 claims description 3
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 3
- 229960000355 copper sulfate Drugs 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- 229960001781 ferrous sulfate Drugs 0.000 claims description 3
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 3
- 239000003077 lignite Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- CFYGEIAZMVFFDE-UHFFFAOYSA-N neodymium(3+);trinitrate Chemical compound [Nd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CFYGEIAZMVFFDE-UHFFFAOYSA-N 0.000 claims description 3
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 3
- 239000004328 sodium tetraborate Substances 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 abstract description 3
- 239000003513 alkali Substances 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 5
- 230000001965 increasing effect Effects 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- 241000196324 Embryophyta Species 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 229910052684 Cerium Inorganic materials 0.000 description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- 235000009849 Cucumis sativus Nutrition 0.000 description 2
- 240000008067 Cucumis sativus Species 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 229910019934 (NH4)2MoO4 Inorganic materials 0.000 description 1
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 description 1
- 208000035240 Disease Resistance Diseases 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 241000233679 Peronosporaceae Species 0.000 description 1
- 229930003268 Vitamin C Natural products 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 229930002875 chlorophyll Natural products 0.000 description 1
- 235000019804 chlorophyll Nutrition 0.000 description 1
- ATNHDLDRLWWWCB-AENOIHSZSA-M chlorophyll a Chemical compound C1([C@@H](C(=O)OC)C(=O)C2=C3C)=C2N2C3=CC(C(CC)=C3C)=[N+]4C3=CC3=C(C=C)C(C)=C5N3[Mg-2]42[N+]2=C1[C@@H](CCC(=O)OC\C=C(/C)CCC[C@H](C)CCC[C@H](C)CCCC(C)C)[C@H](C)C2=C5 ATNHDLDRLWWWCB-AENOIHSZSA-M 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000021749 root development Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 235000019154 vitamin C Nutrition 0.000 description 1
- 239000011718 vitamin C Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05F—ORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C, e.g. FERTILISERS FROM WASTE OR REFUSE
- C05F11/00—Other organic fertilisers
- C05F11/02—Other organic fertilisers from peat, brown coal, and similar vegetable deposits
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Fertilizers (AREA)
Abstract
The invention provides manufacturing equipment and a manufacturing method of a humic acid chelated rare earth water-soluble fertilizer, relates to the technical field of fertilizer manufacturing equipment, and solves the technical problems that in the prior art, the utilization rate and efficiency of an inorganic rare earth compound used alone in plants are low, and the using amount is large. The manufacturing equipment of the humic acid chelated rare earth water soluble fertilizer comprises a humic acid reaction device, a chelation reaction device and a post-treatment device; the humic acid reaction device comprises a humic acid reaction kettle, a centrifugal machine, a filter and a sulfonation reaction kettle which are sequentially arranged, wherein an outlet of the sulfonation reaction kettle is communicated with an inlet of the chelation reaction device. The preparation method comprises the step of reacting the humic acid raw material with alkali, sulfonating agent, rare earth compound and trace element compound in sequence. The invention is used for providing the manufacturing equipment and the manufacturing method for the humic acid chelated rare earth water-soluble fertilizer capable of improving the utilization rate and the efficiency of the rare earth elements.
Description
Technical Field
The invention relates to the technical field of fertilizer manufacturing equipment, in particular to manufacturing equipment and a manufacturing method of a humic acid chelated rare earth water-soluble fertilizer.
Background
Rare earth elements (Rare earth elements) are a general term for lanthanides, and include 17 elements such as cerium, lanthanum, neodymium, and yttrium, which have various special properties such as light, electricity, magnetism, and biochemistry. Researches prove that the rare earth element has multiple functions of enhancing plant photosynthesis, increasing chlorophyll content and activity of multiple enzymes, promoting plant metabolism and root development, promoting absorption and utilization of nutrient elements, improving crop quality, improving stress resistance (sterilization, disease resistance, drought resistance and the like) and the like. The applicant finds that the utilization rate and the efficiency of the inorganic rare earth compound used in plants are low and the dosage is large in the prior art.
Disclosure of Invention
The invention aims to provide manufacturing equipment and a manufacturing method of a humic acid chelated rare earth water-soluble fertilizer, which aim to solve the technical problems of low utilization rate and efficiency and large using amount of inorganic rare earth compounds used in plants in the prior art. The technical effects that can be produced by the preferred technical scheme in the technical schemes of the invention are described in detail in the following. The technical effects that can be produced by the preferred technical scheme in the technical schemes of the invention are described in detail in the following.
In order to achieve the purpose, the invention provides the following technical scheme:
the manufacturing equipment of the humic acid chelated rare earth water-soluble fertilizer provided by the embodiment of the invention comprises a humic acid reaction device, a chelation reaction device and a post-treatment device; wherein the content of the first and second substances,
the humic acid reaction device comprises a humic acid reaction kettle, a centrifugal machine, a filter and a sulfonation reaction kettle which are sequentially arranged, wherein an outlet of the sulfonation reaction kettle is communicated with an inlet of the chelation reaction device; the post-treatment device comprises a dryer, a crusher, a vibrating screen and a finished product packaging system which are arranged in sequence, and an outlet of the chelation reaction device is communicated with an inlet of the dryer.
In a preferred or alternative embodiment, the chelation reaction device is an electrically heated stirred tank reactor.
In a preferred or optional embodiment, the humic acid reaction device further comprises a first conveyor and a second conveyor, wherein the first conveyor is arranged between the centrifuge and the filter and can convey the material output by the centrifuge to the filter, and the second conveyor is arranged between the filter and the chelation reaction device and can convey the material output by the filter to the chelation reaction device.
In a preferred or alternative embodiment, the first and second conveyors are both pipe chain conveyors.
In a preferred or alternative embodiment, the chelation reaction device is communicated with a liquid discharge port.
In a preferred or optional embodiment, the outlets of the humic acid reaction kettle, the sulfonation reaction kettle and the chelation reaction device are respectively provided with an electromagnetic valve.
In a preferred or alternative embodiment, the aftertreatment device further comprises a screw conveyor arranged between the crusher and the vibrating screen and capable of conveying the material output by the crusher to the vibrating screen.
In a preferred or optional embodiment, the post-processing device further comprises a bucket elevator, and the bucket elevator is arranged between the vibrating screen and the finished product packaging system and can convey the materials output by the vibrating screen to the finished product packaging system.
In a preferred or alternative embodiment, the humic acid reaction kettle and the sulfonation reaction kettle are both electrically-heated stirring reaction kettles.
In a preferred or alternative embodiment, the filter is a vacuum filter.
The method for manufacturing the fertilizer by using the manufacturing equipment of the humic acid chelated rare earth water-soluble fertilizer provided by any technical scheme of the invention comprises the following steps:
step A: mixing a NaOH solution and a humic acid raw material according to a mass ratio of 8-15: 1, putting the mixture into a humic acid reaction kettle, adjusting the temperature to 80-90 ℃, reacting for 1-2 hours, and then sequentially passing the reacted liquid through a centrifugal machine and a filter to obtain a pure sodium humate solution;
and B: b, introducing the solution obtained in the step A into a sulfonation reaction kettle, adding a sulfonating agent according to 1-4% of the mass of the solution obtained in the step A, and adjusting the temperature to 90-120 ℃ to react for 1-2 hours to obtain a sulfonated sodium humate solution;
and C: b, introducing the solution obtained in the step B into a chelation reaction device, adding a rare earth compound according to 0.5-1.5% of the mass of the solution obtained in the step B, and reacting for 3-5 h at the temperature of 80-100 ℃ to obtain a humic acid chelated rare earth solution;
step D: c, sequentially passing the solution obtained in the step C through a dryer, a crusher and a vibrating screen, and concentrating and drying to obtain a powdery or granular humic acid rare earth water-soluble fertilizer;
step E: and D, guiding the humic acid rare earth water-soluble fertilizer obtained in the step D into a finished product packaging system, and finishing packaging.
In a preferred or alternative embodiment, the following steps are further included between step C and step D:
step C1: and adding a trace element compound into the chelation reaction device, wherein the addition amount of the trace element compound is 1-3% of the total mass of the solution, and reacting for 0.5-2 h at the temperature of 80-100 ℃ to obtain the humic acid chelated rare earth micro-fertilizer solution.
In a preferable or optional embodiment, the mass ratio of the sulfonated sodium humate, the rare earth element and the trace element after purification is 50-70: 7-10: 15-20.
In a preferable or optional embodiment, the humic acid raw material is weathered coal powder or brown coal powder with the humic acid content of more than or equal to 60%.
In a preferred or alternative embodiment, the sulfonating agent is any one of nitrosulfonic acid, chlorosulfonic acid and sodium p-hydroxybenzenesulfonate.
In a preferred or alternative embodiment, the rare earth compound is any one of rare earth nitrate, cerium nitrate, neodymium nitrate, lanthanum nitrate, and yttrium nitrate, or a combination of any two of them.
In a preferred or optional embodiment, the trace element compound is any 1-4 of ferrous sulfate, manganese sulfate, zinc sulfate, copper sulfate, borax and ammonium molybdate.
Based on the technical scheme, the embodiment of the invention can at least produce the following technical effects:
the invention provides a manufacturing device of a humic acid chelated rare earth water-soluble fertilizer, which comprises a humic acid reaction device, a chelation reaction device and a post-treatment device, wherein in the preparation process, a humic acid raw material can be sequentially subjected to sulfonation reaction in a sulfonation reaction kettle, and is subjected to chelation reaction with rare earth elements and trace element compounds in the chelation reaction device to obtain the humic acid chelated rare earth water-soluble fertilizer, humic acid is used as an organic ligand, inorganic rare earth and trace element compounds are used as inorganic raw materials, the utilization rate and the efficiency of rare earth elements are improved, the usage amount is reduced, and a new thought is provided for preparing the cheap, efficient, safe and multifunctional organic rare earth trace element fertilizer.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
Fig. 1 is a schematic view of manufacturing equipment for a humic acid chelated rare earth water-soluble fertilizer provided in an embodiment of the invention;
FIG. 2 is a flow chart of a manufacturing method of the humic acid chelated rare earth water-soluble fertilizer provided by the invention;
FIG. 3 is an FTIR spectrum of humic acid raw material;
FIG. 4 is an FTIR spectrum of cerium chelated with zinc.
In the figure, 1, a humic acid reaction device; 11. humic acid reaction kettle; 12. a centrifuge; 13. a filter; 14. a sulfonation reaction kettle; 15. a first conveyor; 16. a second conveyor; 2. a chelation reaction device; 21. a liquid discharge port; 3. a post-processing device; 31. a dryer; 32. a crusher; 33. vibrating screen; 34. a finished product packaging system; 35. a screw conveyor; 36. a bucket elevator; 4. an electromagnetic valve.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the examples given herein without any inventive step, are within the scope of the present invention.
The invention provides a manufacturing device for manufacturing humic acid chelated rare earth water-soluble fertilizer, which can improve the utilization rate and efficiency of rare earth elements.
The technical solution provided by the present invention is explained in more detail with reference to fig. 1 to 4.
As shown in fig. 1 to 4, the manufacturing apparatus of humic acid chelated rare earth water soluble fertilizer provided by the embodiment of the present invention includes a humic acid reaction device 1, a chelation reaction device 2, and a post-treatment device 3; wherein the content of the first and second substances,
the humic acid reaction device 1 comprises a humic acid reaction kettle 11, a centrifuge 12, a filter 13 and a sulfonation reaction kettle 14 which are arranged in sequence, wherein the outlet of the sulfonation reaction kettle 14 is communicated with the inlet of the chelation reaction device 2; the post-treatment device 3 comprises a dryer 31, a crusher 32, a vibrating screen 33 and a finished product packaging system 34 which are arranged in sequence, and an outlet of the chelation reaction device 2 is communicated with an inlet of the dryer 31.
The invention provides a manufacturing device of humic acid chelated rare earth water-soluble fertilizer, which comprises a humic acid reaction device 1, a chelation reaction device 2 and a post-treatment device 3, wherein in the preparation process, humic acid raw materials can be sequentially subjected to sulfonation reaction in a sulfonation reaction kettle 14 and chelation reaction with rare earth elements and trace element compounds in the chelation reaction device 2 to obtain the humic acid chelated rare earth water-soluble fertilizer, the humic acid is used as an organic ligand, the inorganic rare earth and the trace element compounds are used as inorganic raw materials, the utilization rate and the efficiency of the rare earth elements are improved, the usage amount is reduced, and a new thought is provided for preparing the cheap, efficient, safe and multifunctional organic rare earth trace element fertilizer.
As a preferred or alternative embodiment, the chelation reaction device 2 is an electrically heated stirred tank reactor. The material is stainless steel, and the volume is preferably 5m3。
As a preferred or alternative embodiment, the humic acid reaction device 1 further comprises a first conveyor 15 and a second conveyor 16, wherein the first conveyor 15 is arranged between the centrifuge 12 and the filter 13 and can convey the material output by the centrifuge 12 to the filter 13, and the second conveyor 16 is arranged between the filter 13 and the chelation reaction device 2 and can convey the material output by the filter 13 to the chelation reaction device 2. Removing the residue to obtain pure sodium humate solution.
As a preferred or alternative embodiment, the first conveyor 15 and the second conveyor 16 are both pipe chain conveyors.
In a preferred or alternative embodiment, the chelation reaction device 2 is communicated with a liquid discharge port 21. The liquid humic acid rare earth micro-fertilizer chelated by the rare earth and the trace elements can be directly led out for packaging and used as a liquid fertilizer.
As a preferred or alternative embodiment, electromagnetic valves 4 are respectively arranged at the outlets of the humic acid reaction kettle 11, the sulfonation reaction kettle 14 and the chelation reaction device 2. The solenoid valve 4 is closed during the reaction, the solenoid valve 4 is opened after the reaction, and the liquid is released to flow into the next reaction device.
As a preferred or alternative embodiment, the aftertreatment device 3 further comprises a screw conveyor 35, the screw conveyor 35 being arranged between the crusher 32 and the vibrating screen 33 and being capable of conveying the material output by the crusher 32 to the vibrating screen 33.
Specifically, the material after the chelation reaction is firstly dried by a dryer 31 to concentrate the solution, then crushed by a crusher 32 to obtain a powdery or granular humic acid rare earth micro-fertilizer, and a product with a mass volume meeting the standard is screened out by a vibrating screen 33 and finally packaged by a finished product packaging system 34; wherein, the dryer 31 can also be a triple-effect evaporator or an MPV high-effect evaporator.
As a preferred or alternative embodiment, the post-processing device 3 further comprises a bucket elevator 36, and the bucket elevator 36 is arranged between the vibrating screen 33 and the finished product packaging system 34 and can convey the materials output by the vibrating screen 33 to the finished product packaging system 34.
As a preferred or alternative embodiment, the humic acid reaction kettle 11 and the sulfonation reaction kettle 14 are both electrically heated stirred reaction kettles.
As a preferred or alternative embodiment, the filter 13 is a vacuum filter.
The method for manufacturing the fertilizer by using the manufacturing equipment of the humic acid chelated rare earth water-soluble fertilizer provided by any technical scheme of the invention comprises the following steps:
step A: mixing a NaOH solution and a humic acid raw material according to a mass ratio of 8-15: 1, putting the mixture into a humic acid reaction kettle 11, adjusting the temperature to 80-90 ℃, reacting for 1-2 hours, and then sequentially passing the reacted liquid through a centrifugal machine 12 and a filter 13 to obtain a pure sodium humate solution;
and B: b, introducing the solution obtained in the step A into a sulfonation reaction kettle 14, adding a sulfonating agent according to 1-4% of the mass of the solution obtained in the step A, and adjusting the temperature to 90-120 ℃ to react for 1-2 hours to obtain a sulfonated sodium humate solution;
and C: b, introducing the solution obtained in the step B into a chelation reaction device 2, adding a rare earth compound according to 0.5-1.5% of the mass of the solution obtained in the step B, and reacting for 3-5 hours at the temperature of 80-100 ℃ to obtain a humic acid chelated rare earth solution;
step D: c, the solution obtained in the step C is sequentially subjected to concentration and drying through a dryer 31, a crusher 32 and a vibrating screen 33 to obtain a powdery or granular humic acid rare earth water-soluble fertilizer;
step E: and D, guiding the humic acid rare earth water-soluble fertilizer obtained in the step D into a finished product packaging system 34, and completing packaging.
As a preferred or alternative embodiment, the following steps are further included between step C and step D:
step C1: and adding a trace element compound into the chelation reaction device 2, wherein the addition amount of the trace element compound is 1-3% of the total mass of the solution, and adjusting the temperature to 80-100 ℃ to react for 0.5-2 h to obtain the humic acid chelated rare earth trace fertilizer solution.
According to a preferable or optional embodiment, the mass ratio of the sulfonated sodium humate, the rare earth element and the trace element after purification is 50-70: 7-10: 15-20.
As a preferable or optional implementation mode, the humic acid raw material is weathered coal powder or brown coal powder with the humic acid content of more than or equal to 60 percent. Preferably weathered coal fines.
In a preferred or alternative embodiment, the sulfonating agent is any one of nitrosulfonic acid, chlorosulfonic acid and sodium p-hydroxybenzenesulfonate. Sodium p-hydroxybenzenesulfonate is preferred.
In a preferred or alternative embodiment, the rare earth compound is any one of rare earth nitrate, cerium nitrate, neodymium nitrate, lanthanum nitrate, and yttrium nitrate, or a combination of any two of them. The substances are all sold in the market, and the chemical formulas of the substances are respectively as follows: re (NO)3·6H2O、Ce(NO)3·6H2O、Nd(NO)3·6H2O、La(NO)3·6H2O、Y(NO)3·6H2O。
In a preferred or optional embodiment, the trace element compound is any 1-4 of ferrous sulfate, manganese sulfate, zinc sulfate, copper sulfate, borax and ammonium molybdate. The chemical formulas of the substances are respectively as follows: fe (SO)4·7H2O、Mn(SO)4·H2O、Zn(SO)4·7H2O、Cu(SO)4·5H2O、NaB4O7·10H2O、(NH4)2MoO4。
The quality indexes of the manufactured humic acid chelated rare earth water-soluble micro-fertilizer are that the content of water-soluble humic acid is more than or equal to 70%, the content of rare earth elements is more than or equal to 1%, the total amount of trace elements is more than or equal to 2%, the pH value is approximately equal to 6-9, the water insoluble substance is less than or equal to 1%, the condensation limit is more than or equal to 10mmol/g, the optimum concentration of the rare earth micro-fertilizer during seed soaking and spraying is 0.5-1 g/L, and the corresponding concentration of the rare earth elements is in the safe use range of 5-50.
Example 1:
adding 1000kg of 1% NaOH solution into a humic acid reaction kettle 11, adding 100kg of weathered coal powder, heating to 90 ℃ under stirring, reacting for 2 hours, transferring into a centrifuge 12 (which can be a horizontal spiral sedimentation centrifuge) for separation, filtering the solution by a filter 13 to obtain 780kg of sodium humate solution (water-insoluble substance is 0.12 g/L), transferring the solution into a sulfonation reaction kettle 14, adding 23kg of sodium p-hydroxybenzenesulfonate, reacting for 2 hours at 97 ℃ to obtain a sulfonated sodium humate solution, adding 8kg of cerium nitrate (Ce (NO) 3.6H 2O) in mass of the sulfonated sodium humate solution into the same reaction kettle, reacting for 3 hours at 90 ℃, adding 17kg of zinc sulfate (Zn (SO) 4.7H 2O), reacting for 1.5 hours at 90 ℃ to obtain a humic acid chelated rare earth micro-fertilizer solution, and drying/granulating by a dryer 31 and a crusher 32 to obtain 82kg of granular humic acid chelated rare earth water-soluble micro fertilizer.
Fourier transform infrared spectroscopy (FTIR) analysis is carried out on the sample, as shown in figures 3-4, compared with figure 3 (humic acid raw material), figure 4 (humic acid rare earth water-soluble micro-fertilizer) is chelated with 1720cm in the spectrogram sample of the micro-fertilizer-1The peak (carboxyl absorption peak) at pH5 shows a significantly smaller area and completely disappeared at pH 8; 1629cm-1、1405cm-1Peaks (respectively asymmetric and symmetric vibration of carboxyl), and the area in the spectrogram of the chelated trace fertilizer is increased; 1234.8cm-1(the deformation vibration of C-O-H of carboxyl, alcohol group and phenolic hydroxyl) is reduced in area at the pH of 5, and completely disappears at the pH of 8, which shows that the carboxyl and the hydroxyl in the humic acid are subjected to complexation or chelation reaction with rare earth cerium and trace element zinc.
Example 2:
the procedure and reaction conditions were essentially the same as in example 1, except that 25kg of nitrosulfonic acid was used as the sulfonating agent, and rare earth nitrate [ Re (NO) ]was used as the rare earth compound3·6H2O]The microelement comprises 6kg ferrous sulfate [ Fe (SO)4·7H2O]4kg of manganese sulfate [ Mn (SO)4·H2O]And 8kg Zinc sulfate [ Zn (SO)4·7H2O]90.6kg of granular humic acid rare earth water-soluble trace fertilizer is obtained.
The humic acid chelated rare earth micro-fertilizer product prepared by the method is prepared into a solution with the concentration of 0.05%, and the result of field plot experiment shows that when the solution is sprayed on cucumbers for 3 times, compared with a control, the yield of the cucumbers is increased by 27.8%, the vitamin C is increased by 15%, the reducing sugar is increased by 27.8%, and the downy mildew incidence is zero (the incidence of the control experiment is 15.6%).
Any embodiment disclosed herein above is meant to disclose, unless otherwise indicated, all numerical ranges disclosed as being preferred, and any person skilled in the art would understand that: the preferred ranges are merely those values which are obvious or representative of the technical effect which can be achieved. Since the numerical values are too numerous to be exhaustive, some of the numerical values are disclosed in the present invention to illustrate the technical solutions of the present invention, and the above-mentioned numerical values should not be construed as limiting the scope of the present invention.
If the terms "first," "second," etc. are used herein to define parts, those skilled in the art will recognize that: the terms "first" and "second" are used merely to distinguish one element from another in a descriptive sense and are not intended to have a special meaning unless otherwise stated.
Meanwhile, if the invention as described above discloses or relates to parts or structural members fixedly connected to each other, the fixedly connected parts can be understood as follows, unless otherwise stated: a detachable fixed connection (for example using bolts or screws) is also understood as: non-detachable fixed connection (such as riveting and welding), of course, the mutual fixed connection can also be an integral structure (for example, the mutual fixed connection is manufactured by casting and integral forming instead (except that the integral forming process can not be adopted obviously).
In addition, terms used in any technical solutions disclosed in the present invention to indicate positional relationships or shapes include approximate, similar or approximate states or shapes unless otherwise stated. Any part provided by the invention can be assembled by a plurality of independent components or can be manufactured by an integral forming process.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention and not to limit it; although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art will understand that: modifications to the specific embodiments of the invention or equivalent substitutions for parts of the technical features may be made; without departing from the spirit of the present invention, it is intended to cover all aspects of the invention as defined by the appended claims.
Claims (10)
1. The manufacturing equipment of the humic acid chelated rare earth water-soluble fertilizer is characterized by comprising a humic acid reaction device, a chelation reaction device and a post-treatment device; wherein the content of the first and second substances,
the humic acid reaction device comprises a humic acid reaction kettle, a centrifugal machine, a filter and a sulfonation reaction kettle which are sequentially arranged, wherein an outlet of the sulfonation reaction kettle is communicated with an inlet of the chelation reaction device; the post-treatment device comprises a dryer, a crusher, a vibrating screen and a finished product packaging system which are arranged in sequence, and an outlet of the chelation reaction device is communicated with an inlet of the dryer.
2. The manufacturing equipment of the humic acid chelated rare earth water soluble fertilizer as claimed in claim 1, wherein the humic acid reaction device further comprises a first conveyor and a second conveyor, the first conveyor is arranged between the centrifuge and the filter and can convey the material output by the centrifuge to the filter, and the second conveyor is arranged between the filter and the chelation reaction device and can convey the material output by the filter to the chelation reaction device; and/or the presence of a gas in the gas,
the post-processing device further comprises a screw conveyor and a bucket elevator, wherein the screw conveyor is arranged on the crusher and can convey the materials output by the crusher to the vibrating screen between the vibrating screen, and the bucket elevator is arranged on the vibrating screen and can convey the materials output by the vibrating screen to the finished product packaging system between the vibrating screen and the finished product packaging system.
3. The manufacturing equipment of the humic acid chelated rare earth water soluble fertilizer as claimed in claim 1, wherein the chelating reaction device is communicated with a liquid discharge port.
4. A method for manufacturing a fertilizer by using the manufacturing equipment of the humic acid chelated rare earth water soluble fertilizer as described in any one of claims 1 to 3, which is characterized by comprising the following steps:
step A: mixing a NaOH solution and a humic acid raw material according to a mass ratio of 8-15: 1, putting the mixture into a humic acid reaction kettle, adjusting the temperature to 80-90 ℃, reacting for 1-2 hours, and then sequentially passing the reacted liquid through a centrifugal machine and a filter to obtain a pure sodium humate solution;
and B: b, introducing the solution obtained in the step A into a sulfonation reaction kettle, adding a sulfonating agent according to 1-4% of the mass of the solution obtained in the step A, and adjusting the temperature to 90-120 ℃ to react for 1-2 hours to obtain a sulfonated sodium humate solution;
and C: b, introducing the solution obtained in the step B into a chelation reaction device, adding a rare earth compound according to 0.5-1.5% of the mass of the solution obtained in the step B, and reacting for 3-5 h at the temperature of 80-100 ℃ to obtain a humic acid chelated rare earth solution;
step D: c, sequentially passing the solution obtained in the step C through a dryer, a crusher and a vibrating screen, and concentrating and drying to obtain a powdery or granular humic acid rare earth water-soluble fertilizer;
step E: and D, guiding the humic acid rare earth water-soluble fertilizer obtained in the step D into a finished product packaging system, and finishing packaging.
5. The method for manufacturing the fertilizer by using the manufacturing equipment of the humic acid chelated rare earth water soluble fertilizer as claimed in claim 4, characterized by further comprising the following steps between the step C and the step D:
step C1: and adding a trace element compound into the chelation reaction device, wherein the addition amount of the trace element compound is 1-3% of the total mass of the solution, and reacting for 0.5-2 h at the temperature of 80-100 ℃ to obtain the humic acid chelated rare earth micro-fertilizer solution.
6. The method for manufacturing the fertilizer by using the manufacturing equipment of the humic acid chelated rare earth water soluble fertilizer as claimed in claim 4, wherein the mass ratio of the sulfonated sodium humate, the rare earth elements and the trace elements after being purified is 50-70: 7-10: 15-20.
7. The method for manufacturing the fertilizer by using the manufacturing equipment of the humic acid chelated rare earth water soluble fertilizer as claimed in claim 4, wherein the humic acid raw material is weathered coal powder or lignite powder with a humic acid content of not less than 60%.
8. The method for manufacturing the fertilizer by using the manufacturing equipment of the humic acid chelated rare earth water soluble fertilizer as claimed in claim 4, wherein the sulfonating agent is any one of nitrosulfonic acid, chlorosulfonic acid and sodium p-hydroxybenzenesulfonate.
9. The method for manufacturing the fertilizer by using the manufacturing equipment of the humic acid chelated rare earth water-soluble fertilizer is characterized in that the rare earth compound is any one of or a combination of any two of rare earth nitrate, cerium nitrate, neodymium nitrate, lanthanum nitrate and yttrium nitrate.
10. The method for manufacturing the fertilizer by using the manufacturing equipment of the humic acid chelated rare earth water soluble fertilizer as claimed in claim 5, wherein the trace element compound is any 1-4 of ferrous sulfate, manganese sulfate, zinc sulfate, copper sulfate, borax and ammonium molybdate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010371182.9A CN111440035B (en) | 2020-05-06 | 2020-05-06 | Equipment and method for manufacturing humic acid chelated rare earth water-soluble fertilizer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010371182.9A CN111440035B (en) | 2020-05-06 | 2020-05-06 | Equipment and method for manufacturing humic acid chelated rare earth water-soluble fertilizer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111440035A true CN111440035A (en) | 2020-07-24 |
| CN111440035B CN111440035B (en) | 2024-06-21 |
Family
ID=71654638
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010371182.9A Active CN111440035B (en) | 2020-05-06 | 2020-05-06 | Equipment and method for manufacturing humic acid chelated rare earth water-soluble fertilizer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111440035B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1169976A (en) * | 1996-07-08 | 1998-01-14 | 中国科学院山西煤炭化学研究所 | High concentrative non-flocculant humic acids complexed nutrient liquid and preparation thereof |
| CN104341195A (en) * | 2013-07-28 | 2015-02-11 | 张苏侠 | Mechanical apparatus for producing base fertilizer special for Chaojinxing haw tree |
| CN107793211A (en) * | 2016-08-31 | 2018-03-13 | 南宁汉和生物科技股份有限公司 | A kind of green synergist for fertilizer agricultural chemicals and preparation method thereof |
| CN109438091A (en) * | 2018-12-28 | 2019-03-08 | 张铮汉 | A kind of preparation method of multielement humic acid chelating fertilizer |
| CN110498717A (en) * | 2018-05-17 | 2019-11-26 | 广西桂平市焱焱肥业有限公司 | A kind of mineral resources potassium fulvate water-soluble fertilizer and preparation method thereof |
| CN212128016U (en) * | 2020-05-06 | 2020-12-11 | 山西同生润洁生物科技有限公司 | Manufacturing equipment of humic acid chelated rare earth water-soluble fertilizer |
-
2020
- 2020-05-06 CN CN202010371182.9A patent/CN111440035B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1169976A (en) * | 1996-07-08 | 1998-01-14 | 中国科学院山西煤炭化学研究所 | High concentrative non-flocculant humic acids complexed nutrient liquid and preparation thereof |
| CN104341195A (en) * | 2013-07-28 | 2015-02-11 | 张苏侠 | Mechanical apparatus for producing base fertilizer special for Chaojinxing haw tree |
| CN107793211A (en) * | 2016-08-31 | 2018-03-13 | 南宁汉和生物科技股份有限公司 | A kind of green synergist for fertilizer agricultural chemicals and preparation method thereof |
| CN110498717A (en) * | 2018-05-17 | 2019-11-26 | 广西桂平市焱焱肥业有限公司 | A kind of mineral resources potassium fulvate water-soluble fertilizer and preparation method thereof |
| CN109438091A (en) * | 2018-12-28 | 2019-03-08 | 张铮汉 | A kind of preparation method of multielement humic acid chelating fertilizer |
| CN212128016U (en) * | 2020-05-06 | 2020-12-11 | 山西同生润洁生物科技有限公司 | Manufacturing equipment of humic acid chelated rare earth water-soluble fertilizer |
Non-Patent Citations (2)
| Title |
|---|
| 曾宪成;: "水溶性腐植酸肥料及其功能", 中国农资, no. 04, 25 January 2013 (2013-01-25) * |
| 李晨璐;郭雅妮;李金成;李璐明;苏海雯;: "磺化腐植酸的制备及其性能测试", 西安工程大学学报, no. 02, 25 April 2020 (2020-04-25) * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111440035B (en) | 2024-06-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN212128016U (en) | Manufacturing equipment of humic acid chelated rare earth water-soluble fertilizer | |
| CN104829342B (en) | A kind of method of allantoin waste water production composite fertilizer | |
| CN101386909A (en) | Method for extracting rare-earth from ardealite | |
| CN102492054B (en) | Preparation method of soybean episperm pectin gel polysaccharide | |
| CN102358726A (en) | Urea sulfate and preparation method thereof | |
| CN106732432B (en) | A kind of chitosan/persimmon tannin composite material and preparation method and the application in Ti recovery | |
| CN103721857B (en) | A kind of preparation method of willemite thing collecting agent | |
| CN111440035A (en) | Manufacturing equipment and manufacturing method of humic acid chelated rare earth water-soluble fertilizer | |
| CN208018345U (en) | Lithium battery tertiary presoma dried dust recovery system | |
| CN101851269B (en) | Preparation method of selenium protein in selenium-rich ganoderma | |
| CN1266794C (en) | Method for preparing manganese-zinc ferrite by using waste zinc-manganese battery | |
| CN116621647B (en) | Method for preparing humic acid slow-release trace element fertilizer by efficiently activating lignite through MOF derivative | |
| WO2018155687A1 (en) | Metal recovery agent, metal compound recovery agent, and method for recovering metal or metal compound | |
| CN1136029A (en) | Treatment of waste liquid of monosodium glutamate | |
| CN109776694A (en) | The preparation method and applications of algal polysaccharide copper, iron, three chelate of zinc | |
| CN108249976A (en) | A kind of method using selenium ore deposit production high-concentration water-soluble foliar fertilizer containing selenium | |
| CN110382109A (en) | For processing the system and method for including the mineral of lanthanide series and producing rare earth oxide | |
| CN1785922A (en) | Amino acid silicon foliage fertilizer | |
| CN1304659A (en) | Comprehensive utilization method of brown coal | |
| CN102276300B (en) | Full-value organic fertilizer for drop irrigation and preparation method thereof | |
| CN1115311A (en) | Method for treatment of rapeseed cake dregs | |
| Bruhn et al. | On-Line pre-concentration of Cr (III) and Mn (II) in FI-FAAS: A critical study involving interference effects and analytical use of an immobilized 8-hydroxyquinoline minicolumn | |
| CN207871825U (en) | Lithium battery tertiary presoma is packed and batch mixing fume recovery system | |
| CN108835400B (en) | Preparation method and production equipment of biomass complex organic selenium | |
| CN102795670B (en) | High-purity manganese sulfide and method for preparing the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |