CN101486604B - Yellow humic acid foliage fertilizer with straw pulping black liquor as raw material by ammonium sulfite process and preparation thereof - Google Patents
Yellow humic acid foliage fertilizer with straw pulping black liquor as raw material by ammonium sulfite process and preparation thereof Download PDFInfo
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- CN101486604B CN101486604B CN2008100138425A CN200810013842A CN101486604B CN 101486604 B CN101486604 B CN 101486604B CN 2008100138425 A CN2008100138425 A CN 2008100138425A CN 200810013842 A CN200810013842 A CN 200810013842A CN 101486604 B CN101486604 B CN 101486604B
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- black liquor
- humic acid
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- yellow humic
- foliage fertilizer
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- 239000003337 fertilizer Substances 0.000 title claims abstract description 101
- 239000010902 straw Substances 0.000 title claims abstract description 75
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 238000000034 method Methods 0.000 title claims description 62
- 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 description 48
- 239000004021 humic acid Substances 0.000 title claims description 48
- 239000002994 raw material Substances 0.000 title claims description 7
- 230000008569 process Effects 0.000 title description 10
- 238000004537 pulping Methods 0.000 title description 5
- 235000013399 edible fruits Nutrition 0.000 claims abstract description 9
- 235000013311 vegetables Nutrition 0.000 claims abstract description 9
- 230000000694 effects Effects 0.000 claims description 60
- 239000007787 solid Substances 0.000 claims description 31
- 239000011573 trace mineral Substances 0.000 claims description 25
- 235000013619 trace mineral Nutrition 0.000 claims description 25
- 238000001704 evaporation Methods 0.000 claims description 24
- 230000008020 evaporation Effects 0.000 claims description 22
- 239000002253 acid Substances 0.000 claims description 19
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical group [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 19
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 18
- 229910052796 boron Inorganic materials 0.000 claims description 16
- 150000003751 zinc Chemical class 0.000 claims description 12
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical group [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 12
- 229960001763 zinc sulfate Drugs 0.000 claims description 12
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 12
- 229910021538 borax Inorganic materials 0.000 claims description 10
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 10
- 239000011790 ferrous sulphate Substances 0.000 claims description 10
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 10
- 239000004328 sodium tetraborate Substances 0.000 claims description 10
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 10
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 10
- 239000004327 boric acid Substances 0.000 claims description 6
- 235000005074 zinc chloride Nutrition 0.000 claims description 5
- 239000011592 zinc chloride Substances 0.000 claims description 5
- 125000005619 boric acid group Chemical group 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 2
- 244000037666 field crops Species 0.000 abstract description 2
- PUKLDDOGISCFCP-JSQCKWNTSA-N 21-Deoxycortisone Chemical compound C1CC2=CC(=O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@@](C(=O)C)(O)[C@@]1(C)CC2=O PUKLDDOGISCFCP-JSQCKWNTSA-N 0.000 abstract 4
- FCYKAQOGGFGCMD-UHFFFAOYSA-N Fulvic acid Natural products O1C2=CC(O)=C(O)C(C(O)=O)=C2C(=O)C2=C1CC(C)(O)OC2 FCYKAQOGGFGCMD-UHFFFAOYSA-N 0.000 abstract 4
- 229940095100 fulvic acid Drugs 0.000 abstract 4
- 239000002509 fulvic acid Substances 0.000 abstract 4
- 239000003895 organic fertilizer Substances 0.000 abstract 1
- 239000007788 liquid Substances 0.000 description 21
- 241000196324 Embryophyta Species 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000007921 spray Substances 0.000 description 6
- 239000000835 fiber Substances 0.000 description 5
- 238000007701 flash-distillation Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- 229910052725 zinc Inorganic materials 0.000 description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 235000008534 Capsicum annuum var annuum Nutrition 0.000 description 3
- 240000008384 Capsicum annuum var. annuum Species 0.000 description 3
- 235000011430 Malus pumila Nutrition 0.000 description 3
- 244000070406 Malus silvestris Species 0.000 description 3
- 235000015103 Malus silvestris Nutrition 0.000 description 3
- 240000007594 Oryza sativa Species 0.000 description 3
- 235000007164 Oryza sativa Nutrition 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 230000007812 deficiency Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000012010 growth Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 235000015097 nutrients Nutrition 0.000 description 3
- 235000016709 nutrition Nutrition 0.000 description 3
- 230000035764 nutrition Effects 0.000 description 3
- 230000000050 nutritive effect Effects 0.000 description 3
- 230000029553 photosynthesis Effects 0.000 description 3
- 238000010672 photosynthesis Methods 0.000 description 3
- 235000009566 rice Nutrition 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000008016 vaporization Effects 0.000 description 3
- 244000025254 Cannabis sativa Species 0.000 description 2
- 235000002566 Capsicum Nutrition 0.000 description 2
- 240000008574 Capsicum frutescens Species 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 230000002939 deleterious effect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 208000006278 hypochromic anemia Diseases 0.000 description 2
- 229920005610 lignin Polymers 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- WQSRXNAKUYIVET-UHFFFAOYSA-N sulfuric acid;zinc Chemical compound [Zn].OS(O)(=O)=O WQSRXNAKUYIVET-UHFFFAOYSA-N 0.000 description 2
- 240000002234 Allium sativum Species 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 244000144730 Amygdalus persica Species 0.000 description 1
- 240000007087 Apium graveolens Species 0.000 description 1
- 235000015849 Apium graveolens Dulce Group Nutrition 0.000 description 1
- 235000010591 Appio Nutrition 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 240000008067 Cucumis sativus Species 0.000 description 1
- 235000010799 Cucumis sativus var sativus Nutrition 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 206010022971 Iron Deficiencies Diseases 0.000 description 1
- 229920001732 Lignosulfonate Polymers 0.000 description 1
- 244000141359 Malus pumila Species 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 108010020943 Nitrogenase Proteins 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 244000018633 Prunus armeniaca Species 0.000 description 1
- 235000009827 Prunus armeniaca Nutrition 0.000 description 1
- 235000006040 Prunus persica var persica Nutrition 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- 244000300264 Spinacia oleracea Species 0.000 description 1
- 235000009337 Spinacia oleracea Nutrition 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 244000098338 Triticum aestivum Species 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 235000021016 apples Nutrition 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000001390 capsicum minimum Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- ATNHDLDRLWWWCB-AENOIHSZSA-M chlorophyll a Chemical group 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
- 210000003763 chloroplast Anatomy 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 230000000881 depressing effect Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 235000004611 garlic Nutrition 0.000 description 1
- 238000003306 harvesting Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 231100000567 intoxicating Toxicity 0.000 description 1
- 230000002673 intoxicating effect Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 230000003050 macronutrient Effects 0.000 description 1
- 235000021073 macronutrients Nutrition 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000001850 reproductive effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000029058 respiratory gaseous exchange Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 208000024891 symptom Diseases 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Fertilizers (AREA)
Abstract
The invention relates to a fulvic acid foliage fertilizer prepared from ammonium sulfite straw pulp black liquor and a preparation method thereof. The fulvic acid foliage fertilizer is mainly prepared by adding a soluble microelement fertilizer into the ammonium sulfite straw pulp black liquor. The fulvic acid foliage fertilizer sprayed on leaf surfaces can improve the crop quality, enhance the crop resistability, promote the earlier ripeness of the crops, and improve the yield of the crops. The fulvic acid foliage fertilizer is a highly effective organic fertilizer suitable for field crops, vegetables and fruit trees.
Description
Technical field
The invention provides a kind of straw pulp black liquor by ammonium sulfite method is Yellow humic acid foliage fertilizer of raw material and preparation method thereof, belongs to straw pulp black liquor and administers the field.
Background technology
More than 80% grass fiber in China's paper industry raw material.Grass fiber papermaking mainly contains two kinds, alkaline process and sulfite pulping, in the sulphite process again based on ammonium salt process.Pulping with ammonium sulfite method is with the lignin effect in ammonium sulphite and the plant fiber material, generates easily molten Sulfite lignin and stripping, to reach the purpose of separated fiber.
Pulping with ammonium sulfite method produces a large amount of black liquor, and the composition of its black liquor also contains element and other organic matters such as ammonium nitrogen, sugar and K, P, Fe, Mg, Mn, Zn and B except ammonium lignin sulfonate.Its CODcr is generally more than 120000mg/L.
As seen, contain the nutritive substance of effect such as abundant organic matter needs in the straw pulp black liquor by ammonium sulfite method, so can be used as the raw material of various fertilizer.At present to the utilization of ammonium salt process black liquor except it is prepared the solid-state fertilizer through a series of processing, mainly be with it directly as liquid fertile, draw to the field or by pipeline with the container accumulating and to be poured into the field and directly to apply fertilizer.But directly use straw pulp black liquor by ammonium sulfite method, can produce some during improper use the deleterious reducing substances of crop; This fertilizer moisture content height simultaneously, effective constituent is low, the transportation cost height.
The present invention has overcome above-mentioned shortcoming, employing adds soluble trace elements fertilizer and prepares Yellow humic acid foliage fertilizer in straw pulp black liquor by ammonium sulfite method, increase effective constituent, add the elementary composition that extra micro-composition can balanced feritilizer, the technology of balance fertilizing is implemented among fertilizer formula, and some deleterious materials also can obtain degraded in the evaporating course simultaneously.
Summary of the invention
The object of the present invention is to provide a kind of Yellow humic acid foliage fertilizer.
Another object of the present invention is to provide a kind of preparation method of above-mentioned Yellow humic acid foliage fertilizer.
A kind of straw pulp black liquor by ammonium sulfite method provided by the invention is the Yellow humic acid foliage fertilizer of raw material, forms for add soluble trace elements fertilizer in straw pulp black liquor by ammonium sulfite method, and the envelope-bulk to weight ratio of the two is 1000ml: 0.2-50g;
Wherein, the pH of described Yellow humic acid foliage fertilizer is 6-10.
Described straw pulp black liquor by ammonium sulfite method is unconcentrated straw pulp black liquor, solid content is 4-15%, degree Beaume is 2-9, pH is that 7-10 or described straw pulp black liquor by ammonium sulfite method are the straw pulp black liquor after concentrating, and solid content is 15.1-65%, and degree Beaume is 9-40, preferred solid content is 30-50%, degree Beaume is 17-31, more preferably solid content 40-47, degree Beaume 25-29.
Described soluble trace elements fertilizer is ferrous salt and zinc salt, and its add-on is to add 0.1-15g and 0.1-20g respectively in every 1000ml straw pulp black liquor by ammonium sulfite method, can be used as the field crop foliage fertilizer, or
Described soluble trace elements fertilizer is boron fertilizer and zinc salt, and its add-on is to add 0.1-15g and 0.1-20g respectively in every 1000ml straw pulp black liquor by ammonium sulfite method, can be used as the leaf of vegetable leaven, or
Described soluble trace elements fertilizer is boron salt, zinc salt and ferrous salt, and its add-on is to add 0.1-15g, 0.1-20g and 0.1-15g respectively in every 1000ml straw pulp black liquor by ammonium sulfite method, can be used as the fruit tree leaves leaven.
Described ferrous salt is a ferrous sulfate; Described zinc salt is zinc sulfate and/or zinc chloride, preferably sulfuric acid zinc; Described boron fertilizer is boric acid and/or borax, preferred borax.
The xanthohumic acid weight content is 1-40% in the described Yellow humic acid foliage fertilizer.
The present invention also provides the preparation method of above-mentioned Yellow humic acid foliage fertilizer, it is characterized in that, soluble trace elements fertilizer is added in the straw pulp black liquor by ammonium sulfite method, stirs, and promptly gets Yellow humic acid foliage fertilizer.
Below the present invention is launched to describe in detail:
A kind of Yellow humic acid foliage fertilizer provided by the present invention forms for add soluble trace elements fertilizer in straw pulp black liquor by ammonium sulfite method, and the envelope-bulk to weight ratio of the two is 1000ml: 0.2-50g.
Wherein, straw pulp black liquor by ammonium sulfite method can be for directly from the straw pulp black liquor of wash hollander, without concentrated excessively, and its degree Beaume 2-9, solid content=4-15%, pH value 7-10; But because the fertilizer moisture content height that obtains this moment, effective constituent is low, the transportation cost height, and therefore preferably with the straw pulp black liquor evaporation concentration, the straw pulp black liquor after obtaining earlier concentrating adds soluble trace elements fertilizer then therein.Straw pulp black liquor solid content after concentrating is 15.1-65%, degree Beaume is 9-40, but consider the mobile relatively poor of black liquor when solid content is too high, the influence of factors such as the energy that need expend is excessive, preferred solid content is 30-50%, degree Beaume is 17-31, more preferably solid content 40-47, degree Beaume 25-29.Owing to there is NH during evaporation concentration
3Volatilization, so the more original black liquor pH of the black liquor of evaporation concentration descends to some extent, in general, the pH of the Yellow humic acid foliage fertilizer of gained is 6-10.
With the straw pulp black liquor by ammonium sulfite method evaporation concentration, preferably use multiple-effect evaporation technology, this is because multiple-effect evaporation technology is thermal source with steam, every steam can be taken away pause moisture in the black liquor of 3-5, the efficient height, and utilize save energy.But along with the increase of multiple-effect evaporator effect number, the unit steam consumption reduces gradually, therefore takes all factors into consideration, and preferably uses five to imitate evaporation technologies.
Below five of the concentrated back straw pulp black liquor of the most preferred solid content 40-47 of the present invention, degree Beaume 25-29 being imitated evaporation technologies introduces in detail:
In order to make full use of the heat of black liquor self, improve the heat energy utilization rate, reduce cost, straw pulp black liquor by ammonium sulfite method can be carried out flash distillation earlier before entering five effect evaporations, preferably carry out 2 flash distillations continuously.Flash distillation makes straw pulp black liquor by ammonium sulfite method produce small amount of steam, and the III after the steam of 2 flash tanks feeds respectively in the step is imitated and the IV single-effect evaporator, can utilize the heat of straw pulp black liquor by ammonium sulfite method self.
The temperature that straw pulp black liquor by ammonium sulfite method flows into flash tank is 60-80 ℃, and after 2 step flash distillations, temperature variation is little, and solid content does not have considerable change, carries out five then and imitates evaporation.
The used equipment of five effect evaporations is quintuple effect evaporator, in the quintuple effect evaporator each is imitated and is divided into three parts usually, topmost is a distribution plate, effect is that black liquor evenly distribute that recycle pump is drawn up is in each pipe, the centre is an air chamber, is the heat exchange area of steam and black liquor, and this regional evapotranspiration of black liquor concentrates, foot is a liquid chamber, and the black liquor after the evaporation concentration flows into this position.
Generally speaking, material in the quintuple effect evaporator can be divided into gas phase and liquid phase two portions, and liquid phase is a black liquor, and gas phase is a steam, straw pulp black liquor by ammonium sulfite method flows into the V single-effect evaporator, concentrated by steam heating, enter the IV single-effect evaporator, concentrated by the steam heating of imitating from III from the IV single-effect evaporator, enter low half concentrated black liquid groove, become low half concentrated black liquid, solid content is 20-25%, and degree Beaume is 11-14.
Low half concentrated black liquid enters II single-effect evaporator and I single-effect evaporator then successively, is heated by steam to enter half concentrated black liquid groove after concentrating, and becomes half concentrated black liquid, and solid content is 30-35%, and degree Beaume is 18-21.
Half concentrated black liquid enters the II effect again successively and I is imitated the black liquor groove, is heated by steam to concentrate promptly to become concentrated black liquid, flows into the concentrated black liquid groove.
The concentrated black liquid solid content is 40-47%, and degree Beaume is 25-29.
In quintuple effect evaporator, gas phase is that the flow direction of steam is just opposite, and purpose is to increase the temperature head between gas phase and liquid phase, improves heat exchanger effectiveness.Wherein, the initial vapor temperature of coming out from vapour generator is 200-210 ℃, pressure=0.8-1MPa, drop to 0.2-0.4MPa, about 140 ℃ through reducing valve, feeding I imitates, the steam of this moment is cleaning steam, after the black liquor of imitating with I carries out heat exchange, become the cleaning water of condensation, the temperature of cleaning water of condensation is 105 ℃-120 ℃, in order to make full use of its heat, it is passed through a flash tank, the steam of flash distillation feeds the II single-effect evaporator, and the cleaning water of condensation of discharge can be used for the pulp washing of pulping process.
The steam of the black liquor vaporizing that I is imitated enters II and imitates, as the heating steam that II is imitated, same, the evaporated vapor that the steam of the black liquor vaporizing that II is imitated is imitated as III, and the like, the steam of II, III, IV, V black liquor vaporizing is dirty steam, because of it is that last effect boiling black liquor produces, after itself and this effect black liquor carries out heat exchange, promptly form foul condensate, the foul condensate that II, III, IV, V are imitated finally is summarised in together, and COD flows to sewage work and handles about 1500mg/L.
The temperature of black liquor is followed successively by in above-mentioned each effect:
100-120 ℃ of I effect, 90-100 ℃ of II effect, 80-90 ℃ of III effect, 70-80 ℃ of IV effect, V are imitated 57-65 ℃;
Each is imitated black liquid wave hairdressing and is respectively:
Each is imitated black liquid wave hairdressing and is respectively:
V is imitated 5-9, IV and is imitated 9-12, III effect 11-14; During for the first time through II effect and I effect, II is imitated 14-17, I and is imitated 18-21; During for the second time through II effect and I effect, II is imitated 23-25, I and is imitated 25-29.
Each pressure of imitating is:
I effect 20-38kPa, II effect-19～0kPa, III effect-58～-40kPa, IV effect-73～-60kPa, V effect-84～-79kPa, all pressure all are relative pressure in the literary composition, relative normal atmosphere.
Each heat exchange area of imitating can be decided on the designing treatment ability, with the designing treatment ability: and 70 tons/h of vaporize water, handle 2000m every day
3Straw pulp black liquor by ammonium sulfite method; Logical quantity of steam is 17.5 tons/h under the normal load, and the heat exchange area of every effect is: I is imitated 1600m
2, II imitates 1200 m
2, III imitates, IV is imitated, V is imitated all is 900m
2
In addition, in design,, often need N in each single-effect evaporator in order to improve heat exchanger effectiveness
2Remove Deng non-condensable gases, this can realize at air chamber and vacuum pipe junction throttling orifice plate being arranged by connect a vacuum pump at the air chamber place, only allow non-condensable gases to pass through, and water vapour can't pass through.
Because straw pulp black liquor by ammonium sulfite method be liquid, wherein contains abundant fertilizer, therefore very suitable be that liquid state fertilizer is made on the basis.Because foliage fertilizer directly absorbs instant effect, plant recovery of nutrient height, can improve crop nutrition content supply situation rapidly, therefore, the present invention is made into foliage fertilizer.In addition, concentration and purity based on macronutrient in the present commodity fertilizer continue to increase, the fertilizer efficiency of trace element is also more and more obvious, as enrich trace element fertilizer and can obviously increase production, increase income and improve product quality, therefore in straw pulp black liquor by ammonium sulfite method, add trace element and can strengthen fertilizer efficiency significantly, improve the yield and quality of crop.
Trace element is meant the very low nutritive element of content in soil and the plant, studies and use more 6 kinds of iron, copper, zinc, manganese, molybdenum, the boron etc. that have at present.Though trace element is few at the crop in-vivo content, has very strong specificity, be the indispensable and alternate mutually of crop growth institute.Therefore, when crop lacked any trace element, growing just was suppressed, and caused the underproduction and quality to descend, serious even total crop failure.Otherwise, if these elements are too much, again intoxicating phenomenon can appear, influence crop yield and quality, also can cause some endemic generation of people, animal.
Boron can promote the normal development of reproductive organ, and an important symptom of boron deficiency is that seed can not normal development, even can not form, thereby influences the harvest of crop.Synthetic and the transportation of sugar has promoter action to boron in the object to doing, and chloroplast(id) is degenerated during boron deficiency, influences photosynthesis.Boron can improve the nitrogenase activity of leguminous crop root nodule bacterium, increases amount of nitrogen fixation.During boron deficiency, root nodule is undeveloped, influences amount of nitrogen fixation.Boron can also strengthen crop anti-adversity.
Zinc can promote crop to carry out photosynthesis, and stagnating appears in crop growth when lacking zinc.
It is indispensable that iron is that chlorophyll forms, and is difficult to shift in the plant body, so blade " chlorosis " is the performance of plant iron deficiency, and this chlorosis at first appears on the young leaflet tablet.In addition, iron is all influential to photosynthesis of plants, respiration.
Based on above-mentioned effect of trace elements, Yellow humic acid foliage fertilizer of the present invention is different according to trace element that is added and amount, can be divided into following three series:
(1) field crop foliage fertilizer
Wherein added soluble trace elements fertilizer is ferrous salt and zinc salt, and its add-on is to add 0.1-15g and 0.1-20g in every 1000ml straw pulp black liquor by ammonium sulfite method; Be applicable to field crops such as corn, wheat, paddy rice, soybean;
(2) leaf of vegetable leaven,
Wherein added soluble trace elements fertilizer is boron fertilizer and zinc salt, and its add-on is to add 0.1-15g and 0.1-20g in every 1000ml straw pulp black liquor by ammonium sulfite method, is applicable to vegetables such as spinach, celery, cucumber, garlic, capsicum;
(3) fruit tree leaves leaven
Wherein added soluble trace elements fertilizer is boron salt, zinc and ferrous salt, and its add-on is to add 0.1-15g, 0.1-20g and 0.1-15g in every 1000ml straw pulp black liquor by ammonium sulfite method, is applicable to fruit trees such as apple, peach, apricot.
Wherein, above-mentioned ferrous salt is a ferrous sulfate; Above-mentioned zinc salt is zinc sulfate and/or zinc chloride, preferably sulfuric acid zinc; Above-mentioned boron fertilizer is boric acid and/or borax, preferred borax.
Xanthohumic acid content is very high in the present invention's series Yellow humic acid foliage fertilizer, can arrive 1-40%, xanthohumic acid wherein derives from straw pulp black liquor by ammonium sulfite method, this is because primary xanthohumic acid, by plant residue under the condition that air and moisture content exist, experienced very long natural process, through partly decomposing and forming. by investigation and analysis, at high temperature, add the process of depressing cooking plant fiber, be equivalent to quicken original natural process, except main generation supplies the paper pulp fiber of paper grade (stock), in its raffinate, also contain a considerable number of xanthohumic acid.Xanthohumic acid content is than content height in the alkaline straw-pulp black liquid in the straw pulp black liquor by ammonium sulfite method.Xanthohumic acid contains the various active group and to the physiologically active substance of plant, is the less macromolecular organic compound of molecular weight, and acidic-group is many, and perviousness is strong, can be dissolved in acid, alkali and water, easily by plant absorbing.It is used in agriculture production widely as non-harmful organic substance, shows as the drought resisting, the cold tolerance that improve farm crop on practical application effect, strengthen the resistance against diseases of crop, stimulate the growth of crop, thereby improve the output of crop, improve the quality of crop.
Yellow humic acid foliage fertilizer of the present invention, with respect to prior art by black liquor make liquid fertile, have the following advantage that has:
1, adds the elementary composition of composition balanced feritilizers such as extra nitrogen, phosphorus, potassium, the technology of balance fertilizing is implemented among fertilizer formula
2, Yellow humic acid foliage fertilizer of the present invention is used the direct absorption in back instant effect, plant recovery of nutrient height, can be improved crop nutrition content supply situation rapidly; Use conveniently, save labor; Nutritive ingredient is many and comprehensive, and fertilizer efficiency is fast, helps crop yield.In plant growth vigorous season, avoided common fertilizer topdress fertilizer nutrient discharge transform slow, fertilizer efficiency is slow, the shortcoming that influences crop yield and quality.
3, can make part objectionable impurities degraded in the straw pulp black liquor in the evaporating concentration process, avoid harm crop.
Embodiment
Embodiment 1
Straw pulp black liquor by ammonium sulfite method degree Beaume 2, solid content=4%, pH value 7; In straw pulp black liquor by ammonium sulfite method, add 0.1g ferrous sulfate and 20g zinc sulfate by every 1000ml; Promptly get Yellow humic acid foliage fertilizer, pH is 7, and the weight percent of xanthohumic acid is 1%, is applicable to field crop.
Embodiment 2
Straw pulp black liquor by ammonium sulfite method degree Beaume 9, solid content=15%, pH value 10; Add 15g boric acid and 0.1g zinc chloride by every 1000ml in straw pulp black liquor by ammonium sulfite method, promptly get Yellow humic acid foliage fertilizer, pH is 10; The weight percent of xanthohumic acid is 7%, is applicable to vegetables.
Embodiment 3
Straw pulp black liquor by ammonium sulfite method degree Beaume 5, solid content=9%, pH value 8; To solid content 15.1%, degree Beaume is 9 with its evaporation concentration; Straw pulp black liquor after obtaining concentrating adds 0.1g borax, 15g ferrous sulfate and 20g zinc sulfate by every 1000ml in the straw pulp black liquor after concentrating; Promptly get Yellow humic acid foliage fertilizer, pH is 7; The weight percent of xanthohumic acid is 8%, is applicable to fruit tree.
Embodiment 4
Straw pulp black liquor by ammonium sulfite method degree Beaume 5, solid content=10, pH value 9; It is carried out evaporation concentration to solid content 65%, and degree Beaume is 40, and the straw pulp black liquor after obtaining concentrating adds 15g ferrous sulfate and 0.1g zinc sulfate by every 1000ml in the straw pulp black liquor after concentrating; Promptly get Yellow humic acid foliage fertilizer, pH is 6; The weight percent of xanthohumic acid is 40%, is applicable to field crop.
Embodiment 5
Straw pulp black liquor by ammonium sulfite method degree Beaume 7, solid content=13%, pH value 8; It is imitated evaporation concentration to solid content 30% with five, and degree Beaume is 25; Straw pulp black liquor after promptly obtaining concentrating; Add 0.1g boric acid and 20g zinc sulfate by every 1000ml in the straw pulp black liquor after concentrating, promptly get Yellow humic acid foliage fertilizer, pH is 6; The weight percent of xanthohumic acid is 15%, is applicable to vegetables.
Embodiment 6
Straw pulp black liquor by ammonium sulfite method degree Beaume 8, solid content=14%, pH value 7; It is imitated evaporation concentration to solid content 50% with five, and degree Beaume is 29; Straw pulp black liquor after promptly obtaining concentrating adds 15g borax, 0.1g ferrous sulfate and 0.1g zinc chloride by every 1000ml in the straw pulp black liquor after concentrating; Promptly get Yellow humic acid foliage fertilizer, pH is 6, and the weight percent of xanthohumic acid is 30%, is applicable to fruit tree.
Embodiment 7
Straw pulp black liquor by ammonium sulfite method degree Beaume 4, solid content=6%, pH value 8; With its five effects evaporation,
The concrete technology of five effect evaporations is as follows:
Each imitates pressure: I is imitated 20kPa, II effect-19kPa, III effect-58kPa, IV effect-73kPa, V effect-84kPa;
Each imitates black liquor temperature: 100 ℃ of I effects, 90 ℃ of II effects, 80 ℃ of III effects, 70 ℃ of IV effects, V are imitated 57 ℃
: each is imitated black liquid wave hairdressing and is respectively: V effect 5, IV effect 9, III imitate 11; During for the first time through II effect and I effect, II effect 14, I imitate 18; During for the second time through II effect and I effect, II effect 23, I imitate 25.
Straw pulp black liquor after promptly obtaining concentrating, solid content 40%, degree Beaume are 25;
Add 5g borax, 10g ferrous sulfate and 6g zinc sulfate by every 1000ml in the straw pulp black liquor after concentrating, promptly get Yellow humic acid foliage fertilizer, pH is 7; The weight percent of xanthohumic acid is 18%, is applicable to fruit tree.
Embodiment 8
Straw pulp black liquor by ammonium sulfite method degree Beaume 4, solid content=6%, pH value 8; With it
With its five effects evaporation,
The concrete technology of five effect evaporations is as follows:
Each imitates pressure: I is imitated 38kPa, and II is imitated 0kPa, III effect-40kPa, IV effect-60kPa, V effect-79kPa;
Each imitates black liquor temperature:
120 ℃ of I effects, 100 ℃ of II effects, 90 ℃ of III effects, 80 ℃ of IV effects, V are imitated 65 ℃
Each is imitated black liquid wave hairdressing and is respectively:
V effect 9, IV effect 12, III imitate 14; During for the first time through II effect and I effect, II effect 17, I imitate 21; During for the second time through II effect and I effect, II effect 25, I imitate 29.
Straw pulp black liquor after promptly obtaining concentrating, solid content 47%, degree Beaume are 29; Add 9g ferrous sulfate and 3g zinc sulfate by every 1000ml in the straw pulp black liquor after concentrating, pH is 8; Promptly get Yellow humic acid foliage fertilizer, the weight percent of xanthohumic acid is 5.2%, is applicable to field crop.
Embodiment 9
Other condition is with embodiment 8
Add 10g boric acid and 13g zinc sulfate by every 1000ml in the straw pulp black liquor after concentrating, promptly get Yellow humic acid foliage fertilizer, pH is 8, and the weight percent of xanthohumic acid is 38%, is applicable to vegetables.
Embodiment 10
Other condition is with embodiment 8
Add 12g borax, 11g ferrous sulfate and 7g zinc sulfate by every 1000ml in the straw pulp black liquor after concentrating,, pH 8 promptly gets Yellow humic acid foliage fertilizer, and pH is 8, and the weight percent of xanthohumic acid is 30%, is applicable to fruit tree.
Experimental example 1
1, test materials and method
Da Qu ratio method, every demonstration test district area 2.0hm are adopted in test
23 processing are established in test altogether, handle 1,2 on the basis of conventional fertilizer application, 1000 times of liquid foliage spray of Yellow humic acid foliage fertilizer that obtain with embodiment 1 and 4 in earlier stage at seedling stage, flower respectively, per hectare consumption 450g; Processing 3 on the basis of conventional fertilizer application, is used the foliage spray of equivalent clear water at seedling stage, flower for contrast respectively in earlier stage.Rice varieties is that sky educates 131 for trying the water.
2, determination of yield result
Table 1
| Handle | Square metre spike number | Plant height cm | Spike length cm | The real grain of fringe number | Thousand seed weight g | Output Kg/hm 2 |
| Embodiment 1 embodiment 4 contrasts | 540.4 582.4 511.2 | 79.1 80.2 77.9 | 15.2 15.6 14.6 | 51.6 52.2 48.3 | 23.9 24.3 23.4 | 7318.5 7644.0 6183.5 |
Test-results shows, uses square metre spike number, plant height, spike length, the real grain of fringe number, thousand seed weight, the output of the paddy rice of product of the present invention and compares than control group, and significant increase is all arranged.Wherein, embodiment contrasts per hectare volume increase 1135.0kg for 1 group, volume increase 18.4%, and embodiment contrasts per hectare volume increase 1460.5, volume increase 23.6%, remarkable in economical benefits for 4 groups.
Experimental example 2
1, experimental cultivar
No. 8 apples of the U.S. are the improved seeds of U.S.'s seed selection
2, test design and method
This test is established 4 and different is used processing, and first three groups with 1000 times of foliage-sprays of foliage fertilizer dilution of embodiment 3,6,7, is established one group of contrast in addition and sprayed clear water respectively.Sub-district area 60m
2(long 30m, wide 2m).There are apple tree 10 strains every sub-district.Leaf dressing is carried out about 10 o'clock of the fine morning.
3, test-results
Table 2
| Repeat | I | II | III | On average | The folding per mu yield |
| Embodiment 3 embodiment 6 embodiment 7 contrasts | 87.6 91.3 91.7 81.7 | 89.0 92.2 91.5 82.4 | 87.2 92.6 91.9 82.2 | 87.93 92.03 91.70 82.0 | 967.23 1012.23 1008.70 902.0 |
As seen, the apple of using the Yellow humic acid foliage fertilizer that embodiment 3,6,7 obtains contrast increase production 7.23%, 12.22%, 11.83% respectively, remarkable in economical benefits.
Experimental example 3
1, for the examination material
(1) for the organic humic acid liquid fertilizer of examination fertilizer: Hui Manfeng 4000mg/kg, mainly contains humic acid and each kind of plant required macroelement and trace element;
The embodiment of the invention 2 and 5 gained Yellow humic acid foliage fertilizers
(2) experimental cultivar
No. five capsicums of Soviet Union green pepper, the development of academy of agricultural sciences, Jiangsu Province Vegetable Research Institute.
2, test method
Test in the 2005-2006 booth and carry out.On October 20th, 2006 grew seedlings in the booth, and November 30 was heeled in nutrition pot, field planting on February 5, wide row space 65cm, little line-spacing 35cm, spacing in the rows 33cm, the high furrow of zanjon.Sub-district final singling 30 strains.Carry out the 1st foliage-spray and handle when the door green pepper blooms, Men Jiaozhi carries out the 2nd foliage-spray when 2cm handles, and the door green pepper carries out the 3rd foliage-spray when gathering handles, and is contrast with the clear water.Phase beginning of gathering is April 25, gather final be July 2, totally 68 days.
3, test-results
The ultimate production of table 3 different treatment
| Handle | Per mu yield kg | Volume increase % |
| Full rich embodiment 2 embodiment of favour 5 contrasts | 2878.2 2952.0 3175.2 2628.0 | 9.52 12.33 20.82 |
As seen, use the Yellow humic acid foliage fertilizer obvious effect of increasing production of the embodiment of the invention 2 and 5.
Claims (12)
1. the Yellow humic acid foliage fertilizer that straw pulp black liquor by ammonium sulfite method is a raw material is characterized in that, forms for add soluble trace elements fertilizer in straw pulp black liquor by ammonium sulfite method, and the envelope-bulk to weight ratio of the two is 1000ml: 0.2-50g; Described straw pulp black liquor by ammonium sulfite method is the straw pulp black liquor after evaporation concentration are imitated in employing five.
2. Yellow humic acid foliage fertilizer according to claim 1 is characterized in that, the pH of described Yellow humic acid foliage fertilizer is 6-10.
3. Yellow humic acid foliage fertilizer according to claim 1 and 2 is characterized in that, described straw pulp black liquor by ammonium sulfite method is the straw pulp black liquor after concentrating, and solid content is 15.1-65%, and degree Beaume is 9-40.
4. Yellow humic acid foliage fertilizer according to claim 3 is characterized in that, solid content is 30-50%, and degree Beaume is 17-31.
5. Yellow humic acid foliage fertilizer according to claim 4 is characterized in that, solid content 40-47, degree Beaume 25-29.
6. Yellow humic acid foliage fertilizer according to claim 1, it is characterized in that, described soluble trace elements fertilizer is ferrous salt and zinc salt, and its add-on is to add 0.1-15g and 0.1-20g respectively in every 1000ml straw pulp black liquor by ammonium sulfite method, can be used as the field crop foliage fertilizer.
7. Yellow humic acid foliage fertilizer according to claim 1 is characterized in that, described soluble trace elements fertilizer is boron fertilizer and zinc salt, and its add-on is to add 0.1-15g and 0.1-20g respectively in every 1000ml straw pulp black liquor by ammonium sulfite method, can be used as the leaf of vegetable leaven.
8. Yellow humic acid foliage fertilizer according to claim 1, it is characterized in that, described soluble trace elements fertilizer is boron salt, zinc salt and ferrous salt, and its add-on is to add 0.1-15g, 0.1-20g and 0.1-15g respectively in every 1000ml straw pulp black liquor by ammonium sulfite method, can be used as the fruit tree leaves leaven.
9. according to claim 6 or 7 or 8 any described Yellow humic acid foliage fertilizers, it is characterized in that described ferrous salt is a ferrous sulfate; Described zinc salt is zinc sulfate and/or zinc chloride; Described boron fertilizer is boric acid and/or borax.
10. Yellow humic acid foliage fertilizer according to claim 9 is characterized in that, described zinc salt is a zinc sulfate; Described boron fertilizer is a borax.
11., it is characterized in that the xanthohumic acid weight content is 1-40% in the described Yellow humic acid foliage fertilizer according to any described Yellow humic acid foliage fertilizer of claim 1-10.
12. the preparation method of any described Yellow humic acid foliage fertilizer of claim 1-11 is characterized in that, in the straw pulp black liquor by ammonium sulfite method after the soluble trace elements fertilizer adding employing five effect evaporation concentration, stirs, and promptly gets Yellow humic acid foliage fertilizer.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1202466A (en) * | 1998-04-17 | 1998-12-23 | 赵德志 | Comprehensive treatment process for papermaking wastewater by using ammonium sulfite method |
| CN1280968A (en) * | 1999-07-16 | 2001-01-24 | 江西贵溪化肥厂 | Process for preparing organic composite N-P-K fertilizer from solidified substance in black paper-making liquid |
| CN1915911A (en) * | 2005-08-19 | 2007-02-21 | 北京中航宏源环境工程技术有限公司 | Method for producing organic fertilizer, organic complex fertilizer by using papermaking black liquor through alkaline process including process of sodium sulfite |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1202466A (en) * | 1998-04-17 | 1998-12-23 | 赵德志 | Comprehensive treatment process for papermaking wastewater by using ammonium sulfite method |
| CN1280968A (en) * | 1999-07-16 | 2001-01-24 | 江西贵溪化肥厂 | Process for preparing organic composite N-P-K fertilizer from solidified substance in black paper-making liquid |
| CN1915911A (en) * | 2005-08-19 | 2007-02-21 | 北京中航宏源环境工程技术有限公司 | Method for producing organic fertilizer, organic complex fertilizer by using papermaking black liquor through alkaline process including process of sodium sulfite |
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