CN115874477B - Water-soluble fertilizer product prepared from pulping byproducts and application thereof - Google Patents
Water-soluble fertilizer product prepared from pulping byproducts and application thereof Download PDFInfo
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- CN115874477B CN115874477B CN202111155518.9A CN202111155518A CN115874477B CN 115874477 B CN115874477 B CN 115874477B CN 202111155518 A CN202111155518 A CN 202111155518A CN 115874477 B CN115874477 B CN 115874477B
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- fertilizer
- weight
- calcium
- potassium
- solution
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- 239000003337 fertilizer Substances 0.000 title claims abstract description 363
- 238000004537 pulping Methods 0.000 title claims abstract description 78
- 239000000047 product Substances 0.000 title claims abstract description 27
- 239000006227 byproduct Substances 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 134
- 229920005610 lignin Polymers 0.000 claims abstract description 88
- 239000002253 acid Substances 0.000 claims abstract description 55
- 230000008569 process Effects 0.000 claims abstract description 39
- 239000003513 alkali Substances 0.000 claims abstract description 31
- 229920001732 Lignosulfonate Polymers 0.000 claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 claims abstract description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 120
- RYAGRZNBULDMBW-UHFFFAOYSA-L calcium;3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Ca+2].COC1=CC=CC(CC(CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O RYAGRZNBULDMBW-UHFFFAOYSA-L 0.000 claims description 100
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 87
- 239000011591 potassium Substances 0.000 claims description 87
- 229910052700 potassium Inorganic materials 0.000 claims description 87
- 229920005551 calcium lignosulfonate Polymers 0.000 claims description 82
- 239000000243 solution Substances 0.000 claims description 74
- 239000007788 liquid Substances 0.000 claims description 73
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 62
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 51
- 239000000843 powder Substances 0.000 claims description 41
- JXRVKYBCWUJJBP-UHFFFAOYSA-L calcium;hydrogen sulfate Chemical compound [Ca+2].OS([O-])(=O)=O.OS([O-])(=O)=O JXRVKYBCWUJJBP-UHFFFAOYSA-L 0.000 claims description 34
- 239000002994 raw material Substances 0.000 claims description 31
- 238000010025 steaming Methods 0.000 claims description 26
- 229910052757 nitrogen Inorganic materials 0.000 claims description 25
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 21
- 229910052698 phosphorus Inorganic materials 0.000 claims description 21
- 239000011574 phosphorus Substances 0.000 claims description 21
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 20
- 239000007787 solid Substances 0.000 claims description 19
- 239000000706 filtrate Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 238000002791 soaking Methods 0.000 claims description 17
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- 238000001914 filtration Methods 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 16
- 230000001105 regulatory effect Effects 0.000 claims description 14
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 13
- 239000011575 calcium Substances 0.000 claims description 13
- 229910052791 calcium Inorganic materials 0.000 claims description 13
- 238000001694 spray drying Methods 0.000 claims description 13
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 12
- 239000000920 calcium hydroxide Substances 0.000 claims description 12
- 235000011116 calcium hydroxide Nutrition 0.000 claims description 12
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 12
- GBAOBIBJACZTNA-UHFFFAOYSA-L calcium sulfite Chemical compound [Ca+2].[O-]S([O-])=O GBAOBIBJACZTNA-UHFFFAOYSA-L 0.000 claims description 12
- 235000010261 calcium sulphite Nutrition 0.000 claims description 12
- YAECNLICDQSIKA-UHFFFAOYSA-L calcium;sulfanide Chemical compound [SH-].[SH-].[Ca+2] YAECNLICDQSIKA-UHFFFAOYSA-L 0.000 claims description 12
- 238000004898 kneading Methods 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 11
- 239000005416 organic matter Substances 0.000 claims description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 10
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 9
- 238000010168 coupling process Methods 0.000 claims description 9
- 239000011593 sulfur Substances 0.000 claims description 9
- 229910052717 sulfur Inorganic materials 0.000 claims description 9
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 8
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 8
- 229910001424 calcium ion Inorganic materials 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 238000006386 neutralization reaction Methods 0.000 claims description 8
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 8
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 8
- 235000011151 potassium sulphates Nutrition 0.000 claims description 8
- 230000001502 supplementing effect Effects 0.000 claims description 8
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 7
- 230000008878 coupling Effects 0.000 claims description 7
- 238000005859 coupling reaction Methods 0.000 claims description 7
- 239000003516 soil conditioner Substances 0.000 claims description 7
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 6
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 claims description 6
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 claims description 5
- 229910001950 potassium oxide Inorganic materials 0.000 claims description 5
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 5
- 238000000354 decomposition reaction Methods 0.000 claims description 4
- 238000007865 diluting Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000004064 recycling Methods 0.000 claims description 4
- 235000013619 trace mineral Nutrition 0.000 claims description 4
- 239000011573 trace mineral Substances 0.000 claims description 4
- 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 claims description 3
- WZLMXYBCAZZIRQ-UHFFFAOYSA-N [N].[P].[K] Chemical compound [N].[P].[K] WZLMXYBCAZZIRQ-UHFFFAOYSA-N 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 3
- 239000004021 humic acid Substances 0.000 claims description 3
- 239000011268 mixed slurry Substances 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 3
- 229920005550 ammonium lignosulfonate Polymers 0.000 claims description 2
- 230000001276 controlling effect Effects 0.000 claims description 2
- 239000012263 liquid product Substances 0.000 claims description 2
- 150000003871 sulfonates Chemical class 0.000 claims description 2
- 238000006277 sulfonation reaction Methods 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 239000002689 soil Substances 0.000 abstract description 83
- 238000012545 processing Methods 0.000 abstract description 5
- 244000037666 field crops Species 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 abstract 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 abstract 1
- 241000196324 Embryophyta Species 0.000 description 41
- 235000015097 nutrients Nutrition 0.000 description 35
- 229940072033 potash Drugs 0.000 description 33
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 33
- 235000015320 potassium carbonate Nutrition 0.000 description 33
- 230000000694 effects Effects 0.000 description 22
- 239000002002 slurry Substances 0.000 description 18
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 17
- 235000011941 Tilia x europaea Nutrition 0.000 description 17
- 239000004571 lime Substances 0.000 description 17
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 16
- 235000017491 Bambusa tulda Nutrition 0.000 description 16
- 241001330002 Bambuseae Species 0.000 description 16
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 16
- 239000011425 bamboo Substances 0.000 description 16
- 238000011282 treatment Methods 0.000 description 16
- 235000013399 edible fruits Nutrition 0.000 description 14
- 238000012360 testing method Methods 0.000 description 13
- 229910052602 gypsum Inorganic materials 0.000 description 12
- 239000010440 gypsum Substances 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 11
- 235000002566 Capsicum Nutrition 0.000 description 10
- 230000001580 bacterial effect Effects 0.000 description 10
- 239000010902 straw Substances 0.000 description 10
- 241001122767 Theaceae Species 0.000 description 9
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- 239000000203 mixture Substances 0.000 description 7
- 241000894006 Bacteria Species 0.000 description 6
- 238000005904 alkaline hydrolysis reaction Methods 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- 230000004720 fertilization Effects 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000002028 Biomass Substances 0.000 description 5
- 240000008574 Capsicum frutescens Species 0.000 description 5
- 241000233866 Fungi Species 0.000 description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 5
- 239000011324 bead Substances 0.000 description 5
- 239000001390 capsicum minimum Substances 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical group [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 5
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- 239000010931 gold Substances 0.000 description 5
- 239000003895 organic fertilizer Substances 0.000 description 5
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- 235000019252 potassium sulphite Nutrition 0.000 description 5
- 230000001737 promoting effect Effects 0.000 description 5
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- 206010016807 Fluid retention Diseases 0.000 description 4
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- 235000008184 Piper nigrum Nutrition 0.000 description 4
- RYYVLZVUVIJVGH-UHFFFAOYSA-N caffeine Chemical compound CN1C(=O)N(C)C(=O)C2=C1N=CN2C RYYVLZVUVIJVGH-UHFFFAOYSA-N 0.000 description 4
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- 239000004460 silage Substances 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- 241001494508 Arundo donax Species 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
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- 238000005303 weighing Methods 0.000 description 1
Abstract
The invention relates to a water-soluble fertilizer product prepared from pulping byproducts and application thereof, in particular to a process for preparing a biological-based water-soluble fertilizer by processing red liquor and black liquor obtained by an acid pulping process and an alkali pulping process, wherein the main components of the two water-soluble fertilizers are lignin sulfonate and lignin potassium salt of high polymers, and the water-soluble fertilizer can be widely applied to commercial crops and field crops such as greenhouse, field, desert, saline-alkali soil, barren slopes and the like.
Description
Technical Field
The technology belongs to the field of fertilizer preparation by biomass deep processing and fertilizer application, and in particular relates to a water-soluble fertilizer product prepared from pulping byproducts and application thereof.
Background
Chemical pulping such as alkaline process, acid process, sulfate and the like, including mechanical pulping, semi-mechanical pulping and microbial pulping are limited by a plurality of factors such as raw materials, investment, process, cost, quality, efficiency, environmental protection and the like to face development bottlenecks, and particularly pulping black liquor cannot expand effective use, and the existing alkali recovery or lignin sulfonate recovery has high cost, secondary pollution and needs technical innovation.
The research and development team previously invents a new sectional type pulping process with potassium hydroxide or potassium sulfate/lime combination and no black liquor, and adopts a new process of pre-soaking and short-time low-temperature steaming, so that the consumption of alkali is greatly reduced, the macromolecular structures such as lignin, hemicellulose and the like are prevented from being damaged, substances harmful to soil and plants such as sodium sulfide, sodium ions and the like are prevented from being added, the application of the black liquor as a safe and efficient slow-release potassium-rich organic fertilizer is expanded, and the problems are well solved. However, the production process of co-producing the potassium-rich organic fertilizer by the potassium method still has the problems of high cost of potassium hydroxide, high cost of lignin potassium fertilizer, mobile capital occupation due to sales seasons and product backlog, and the like.
The black liquor-free pulping process is developed to overcome the defect, and can be flexibly switched or operated simultaneously with the potassium process according to market demand change. The black liquor-free pulping process is characterized in that through acidification of a mixture of black liquor and pulp, lignin can be uniformly precipitated on the surface of the pulp, so that not only can the pulp yield and pulp quality be remarkably improved, but also the lipophilicity and antibacterial property of natural color pulp can be improved, and the mother liquor can be repeatedly used, and potassium sulfate contained in the mother liquor can be added into lime milk to carry out double decomposition reaction and neutralization linkage reaction with lignin in plant raw materials, so that balance can be broken and the conversion of the raw materials can be thoroughly promoted. However, although the pulping process without black liquor maintains the cost advantage of low-cost lime pulping, and shortens the traditional lime soaking pulping for hundred days to heating, steaming and boiling for four hours to grind pulp, thereby avoiding producing fertilizer and greatly reducing pulping cost, compared with the potassium pulping process, the pulping process still has the problems of long steaming time, difficult gypsum filtration and washing, low pulp strength, and adhesion of byproduct gypsum to pulp, particularly the production problems affecting production and application such as separation and effective utilization of gypsum, and the like, are still needed to be broken.
Disclosure of Invention
In order to solve the technical problems, the invention stops a novel method for pulping by using a novel acid method and a novel alkali method and coupling of raw materials of the acid method and the alkali method to produce a water-soluble fertilizer simultaneously, the method takes plant raw materials, slaked lime and sulfur dioxide as raw materials, potassium hydroxide or regenerated potassium hydroxide solution as an alkaline resolving agent and calcium bisulfide as an active component and an acid resolving agent to independently pulp and respectively pulp and co-produce a bio-based water-soluble fertilizer by using the acid method and the alkali method, and the method comprises the following steps: (1) Firstly pulping by a potassium hydroxide alkaline method, then precipitating and recovering lignin or lignin and natural color pulp mixed slurry from a solution rich in high molecular lignin potassium by using sulfur dioxide or sulfurous acid solution, and then carrying out mixed double decomposition reaction on the neutralization filtrate and slaked lime to regenerate potassium hydroxide aqueous solution for recycling in the alkaline method to pulping; (2) The precipitated and separated calcium sulfite solid is mixed with mechanically applied acid pulping liquid, sulfur dioxide is continuously introduced or a sulfurous acid solution is added to be converted into a calcium bisulfate solution with excellent water solubility, and the calcium sulfite solution is used as an acid resolving agent in the acid pulping to obtain high-quality natural color pulp with high yield, and a byproduct of high-efficiency green calcium lignosulfonate water-soluble fertilizer or a soil conditioner is obtained, wherein the acid pulping is a pulping method by using the sulfuric acid-containing calcium bisulfate solution as a resolving agent.
The invention also provides a fertilizer, wherein the weight percentage of organic matters in the fertilizer is more than or equal to 60% of the dry weight of the fertilizer, the weight percentage of total nitrogen in the fertilizer is more than or equal to 0.3%, the weight percentage of phosphorus in phosphorus pentoxide in the fertilizer is more than or equal to 0.1%, the weight percentage of potassium in the fertilizer is more than or equal to 1%, the weight percentage of calcium ions in the fertilizer is more than or equal to 9.45%, and the weight percentage of sulfur element in the fertilizer is more than or equal to 7.49%.
Preferably, the fertilizer is obtained by producing slurry by an acid method, producing slurry by an alkali method or producing slurry by an acid-base method in a combined way.
Preferably, in the fertilizer, the organic matters in the fertilizer account for 60% -96% by weight of the dry weight of the fertilizer, the total nitrogen accounts for 0.3% -0.5% by weight of the dry weight of the fertilizer, the phosphorus accounts for 0.1% -0.6% by weight of the dry weight of the fertilizer in terms of phosphorus pentoxide, the potassium accounts for 1% -15% by weight of the dry weight of the fertilizer in terms of potassium oxide, the calcium ions account for 1% -10% by weight of the dry weight of the fertilizer, and the sulfur element accounts for 1% -10% by weight of the dry weight of the fertilizer.
Preferably, in the fertilizer, the fertilizer contains one or more components of potassium lignin, calcium lignin sulfonate or potassium lignin sulfonate.
Preferably, in the fertilizer, the weight of organic matters in the fertilizer accounts for 60-70% of the dry weight of the fertilizer, the weight of potassium in terms of potassium oxide accounts for 9-15% of the dry weight of the fertilizer, and the fertilizer contains potassium lignin.
Preferably, in the fertilizer, the weight of organic matters in the fertilizer accounts for 90-96% of the dry weight of the fertilizer, the weight of sulfur elements accounts for 1-10% of the dry weight of the fertilizer, the fertilizer contains calcium lignosulfonate, the weight of calcium ions accounts for 1-10% of the dry weight of the fertilizer, and the fertilizer contains calcium lignosulfonate.
Preferably, in the fertilizer, the fertilizer is prepared by the following method:
soaking and steaming plant materials in 15% potassium hydroxide solution with the solid mass not lower than that of the plant materials at 80-150 ℃ for 1-3 h, kneading and pulping to obtain unbleached pulp and black liquor, acidifying the black liquor with sulfur dioxide or sulfurous acid solution, adding lime or slaked lime, filtering and separating to obtain liquid, concentrating the liquid to a dry matter content of more than 50% or spray drying to obtain powder, wherein the concentrated liquid or powder is fertilizer, or a mixture of unbleached pulp and black liquor is introduced with sulfur dioxide or added with sulfurous acid solution, acidifying to pH value of 1-5, filtering and separating to obtain unbleached pulp and filtrate rich in lignin, the filtrate contains potassium sulfite, adding lime or slaked lime slurry into the filtrate, stirring and mixing, taking supernatant or filtrate containing potassium hydroxide as alkaline resolving agent of an alkaline process to continuously pulp for the next batch of plant materials, circularly applying and saturating to obtain concentrated liquid or spray drying to obtain concentrated liquid or powder, wherein the concentrated liquid or powder is fertilizer, and the concentrated liquid or powder containing lignin potassium is obtained by concentrating the liquid to the dry matter content of more than 50% after circularly applying.
Or, the black liquor after filtration and separation is directly neutralized or is extracted for neutralization, the pH value is adjusted to 6-8, and then the black liquor is concentrated to concentrated liquid with the dry matter weight content of more than 50 percent or is spray-dried to form powder, and the concentrated liquid or the powder is the fertilizer.
Preferably, the neutralization step is performed using sulfur dioxide or sulfurous acid solution.
In the fertilizer, the fertilizer is prepared by the following method:
according to the solid-to-liquid ratio of the mass of the folded plant material to the calcium bisulfate solution of 1:3-10, the dosage of the calcium bisulfate in the calcium bisulfate solution is 5-15% of the mass of the folded plant, the pH value of the calcium bisulfate solution is adjusted to 1-5 by sulfuric acid, the soaking and steaming temperature is 80-130 ℃ and the steaming time is 2-6 hours, the solution after kneading, pulping, washing and filtering is red liquid taking calcium lignosulfonate as a main component according to a conventional pulping method, or the red liquid is circularly used after supplementing the calcium bisulfate, and the solution containing the calcium lignosulfonate as a byproduct is concentrated to a concentrated liquid with the dry matter weight content of more than 50% after the saturated cyclic application or is spray dried to form powder concentrated liquid or powder, thus obtaining the fertilizer; or adding potassium sulfate into the red liquid, separating precipitated calcium sulfate and solution containing potassium lignin sulfonate, concentrating the solution to obtain concentrated liquid with dry matter content of above 50% or spray drying to obtain powder, and concentrating the liquid or powder to obtain the fertilizer.
Preferably, the calcium bisulfide used in the step of supplementing the calcium bisulfide is prepared by mixing sulfur dioxide gas or sulfur dioxide liquid with lime or slaked lime.
Preferably, in the fertilizer, the red liquid is directly neutralized or extracted for neutralization, and is concentrated to concentrated liquid with the dry matter weight content of more than 50% or is spray-dried to form powder, wherein the concentrated liquid or the powder is the fertilizer.
Preferably, in the fertilizer, the fertilizer is prepared by mixing black liquor of alkaline pulping and red liquor of acid pulping, neutralizing to a proper pH value, concentrating to obtain concentrated liquid with the dry matter weight content of more than 50 percent or spray drying to obtain powder concentrated liquid or powder,
the preparation method of the black liquor comprises the following steps: soaking and steaming plant materials in 15% potassium hydroxide solution with the temperature of 80-150deg.C for 1-3 h, kneading, pulping to obtain unbleached pulp and black liquor, and filtering to obtain black liquor;
the preparation method of the red liquid comprises the following steps: according to the solid-to-liquid ratio of the mass of the folded plant material to the calcium bisulfate solution of 1:3-10, the dosage of the calcium bisulfate in the calcium bisulfate solution is 5-15% of the mass of the folded plant, the pH value of the calcium bisulfate solution is regulated to 1-5 by sulfuric acid, the soaking and steaming temperature is 80-130 ℃ and the steaming time is 2-6 hours, and then the filtrate obtained by rubbing, pulping, washing and filtering is red liquid according to the conventional pulping method.
The invention also provides a mixed fertilizer containing the fertilizer produced by the slurry prepared by the acid method or the alkali method, which is characterized by comprising the fertilizer produced by the slurry prepared by the acid method or the alkali method and one or more of humic acid, macroelement fertilizer, secondary element fertilizer and trace element fertilizer.
Preferably, in the mixed fertilizer, the fertilizer produced by the slurry prepared by an acid method or an alkali method accounts for 30-95% of the weight of the mixed fertilizer.
The invention also provides application of the fertilizer produced by the slurry prepared by the acid method or the alkali method, wherein the fertilizer is used for improving the quantity of soil bacterial groups for crop growth, improving the acid-base environment of soil for crop growth, improving the soil organic matters for crop growth, improving the content of alkaline hydrolysis nitrogen for crop growth, promoting crop growth, improving crop yield and improving crop quality.
The invention also provides a method for preparing the water-soluble fertilizer, which takes plant raw materials, lime, plant ash and sulfur dioxide as raw materials, takes potassium hydroxide, plant ash, potassium sulfate, potassium sulfite or regenerated potassium hydroxide solution as an alkaline resolving agent and calcium bisulfide as an active component and takes an acid resolving agent to independently prepare two kinds of slurry and co-produce two kinds of bio-based water-soluble fertilizers respectively through the processes of independent pulping, acid method and alkali method coupling, and the production steps of the two kinds of fertilizers are as follows:
The acid method for co-producing the calcium-based water-soluble fertilizer comprises the following steps: according to the solid-to-liquid ratio of the mass of the absolute dry plant raw material to the calcium bisulfate solution of 1:3-10, the dosage of the calcium bisulfate in the calcium bisulfate solution is 5-15% of the mass of the absolute dry plant, the pH value of the calcium bisulfate solution is regulated to 1-5 by sulfuric acid, the soaking and steaming temperature is 80-130 ℃ and steaming time is 2-6 hours, the conventional pulping method is used for kneading, pulping, filtering, washing, filtering filtrate to obtain red liquid with calcium lignosulfonate as a main component, the red liquid is circularly used after supplementing the calcium bisulfate and regulating the pH value, and the solution is regulated to 6-8 after being circularly used until nearly saturated, so that the liquid product with the solid content of more than 50% can be directly diluted for use or concentrated into a powder product with the calcium lignosulfonate as the main component by spray drying; or the solution after the pH is regulated is proportioned with potassium sulfate or ammonium sulfate according to the requirement, precipitated calcium sulfate is separated out, and the solution meeting the requirement of the content of potassium lignosulfonate or ammonium lignosulfonate is obtained, and can be directly diluted for use or concentrated to concentrated liquid with the dry matter weight content of more than 50 percent or spray-dried to form a biobased sulfonate series powder water-soluble fertilizer product.
The coupling process of the alkaline method and the acid method comprises the following steps: the method comprises the steps of mixing absolute dry plant raw materials with potassium hydroxide solution according to a solid-to-liquid ratio of 1:3-10, wherein the dosage of the potassium hydroxide is 10-15% of the absolute dry plant mass, the concentration of the potassium hydroxide is about 3%, the soaking and steaming temperature is 80-130 ℃, the steaming time is 0.5-6h, kneading, pulping, filtering and washing filtrate serving as a main component of potassium lignin by a conventional pulping method, supplementing the potassium hydroxide, circularly applying the potassium hydroxide to near saturation, controlling the pH value of the solution to be below 10, directly diluting the solution or concentrating the solution into liquid with the solid content of more than 50%, or spray drying the solution into powder, namely the acid soil conditioner and the bio-based water-soluble fertilizer which are mainly composed of the potassium lignin, soaking, steaming, kneading and pulping the separated black liquor by potassium hydroxide, introducing sulfur dioxide or adding a sulfurous acid solution to acidizing the pH value to 8-9, heating the black liquor to 160 ℃ for 2-3 h sulfonation reaction, and synthesizing the potassium lignin sulfonate, and then serving as a liquid fertilizer or a liquid fertilizer raw material.
Preferably, in the method, the bio-based calcium sulfonate water-soluble fertilizer produced by the co-production bio-based calcium sulfonate water-soluble fertilizer acid process and the lignin potassium water-soluble fertilizer produced by the alkaline process can be used singly or in combination with each other or in combination with the nitrogen-phosphorus-potassium fertilizer; the product has excellent functions of preserving fertilizer and water, supplying fertilizer and absorbing water, providing comprehensive and balanced nutrition, has remarkable effects of improving the yield and quality of crops, increasing the quantity of soil flora, the content of soil organic matters and water-soluble nutrient elements, and regulating the pH value and EC value of soil, and can be developed into a series of products with multiple functions of sand fixation and skinning, alkali inhibition by binding salt, complexation dissolution assistance, ecological restoration and the like, and the product can be used as a series of biological nutrient sources such as safe, cheap and ecological green deserts, saline-alkali lands, fields, facility agriculture, gardens, acid-alkali soil conditioning, nutrient media, edible fungus culture media and the like.
Preferably, in the method, the water-soluble fertilizer co-produced by an alkaline process and an acid process can be used for producing one or more products of humic acid fertilizer, macroelement fertilizer, medium element fertilizer and trace element fertilizer; producing liquid fertilizer, powder fertilizer, granular fertilizer and configuration fertilizer with good sustained and controlled release, water absorption and water retention and comprehensive nutrition and energy supplement; the calcium lignosulfonate product has the functions of dissolution and precipitation resistance, the proportion of each material in the product comprising chemical fertilizer, medium trace fertilizer and organic fertilizer can be adjusted according to nutrient requirements or actual application scenes, the mixture can be mixed or independently applied, and the lignin potassium fertilizer is suitable to be independently applied; in the water-soluble fertilizer or compound fertilizer product, the weight percentage of organic matters can be 40% -96% of the dry weight of the fertilizer, the weight percentage of total nitrogen is 0.3% -5.0% of the dry weight of the fertilizer, the weight percentage of phosphorus in terms of phosphorus pentoxide is 0.1% -5.0% of the dry weight of the fertilizer, the weight percentage of potassium in terms of potassium oxide is 0.5% -15.0% of the dry weight of the fertilizer, the weight percentage of calcium ions is 0.5% -15% of the dry weight of the fertilizer, and the weight percentage of sulfur elements is 0.5% -10% of the dry weight of the fertilizer.
The invention also provides a method for preparing fertilizer by alkaline pulping, which comprises the following steps:
soaking and steaming plant materials in 15% potassium hydroxide solution with the solid mass not lower than 80-150 ℃ for 1-3 h, kneading and pulping to obtain unbleached pulp and black liquor, acidifying the black liquor with sulfur dioxide or sulfurous acid solution, adding lime or slaked lime, filtering and separating to obtain liquid with the dry matter content of more than 50%, concentrating the liquid or spray drying to obtain powder, wherein the concentrated liquid or powder is fertilizer, or the mixture of unbleached pulp and black liquor is introduced with sulfur dioxide or sulfurous acid solution to the pH of 1-5, filtering and separating to obtain lignin-enriched unbleached pulp and filtrate, the filtrate contains potassium sulfite, the filtrate is added with lime or slaked lime slurry for stirring and mixing, the supernatant or filtrate containing potassium hydroxide is used as alkaline resolving agent in the alkaline process for continuously pulping the next batch of plant materials, and neutralizing after cyclic application and saturation, the liquid containing potassium lignin is concentrated to the concentrated liquid with the dry matter content of more than 50% or spray drying to obtain powder concentrated liquid or powder, namely fertilizer.
The invention also provides a method for preparing fertilizer by acid pulping, which comprises the following steps:
according to the solid-to-liquid ratio of the mass of the folded plant material to the calcium bisulfate solution of 1:3-10, the dosage of the calcium bisulfate in the calcium bisulfate solution is 5-15% of the mass of the folded plant, the pH value of the calcium bisulfate solution is adjusted to 1-5 by sulfuric acid, the soaking and steaming temperature is 80-130 ℃ and the steaming time is 2-6 hours, the solution is kneaded, ground, washed and filtered according to the conventional pulping method, the filtrate is red liquid taking calcium lignosulfonate as the main component, the red liquid is circularly used after supplementing the calcium bisulfate, and the solution containing the calcium lignosulfonate as a byproduct is concentrated to a concentrated liquid with the dry matter weight content of more than 50% after the saturated cyclic application, or the concentrated liquid is spray-dried to form powder, and the powder is the fertilizer; or adding potassium sulfate into the red liquid, separating precipitated calcium sulfate and solution containing potassium lignin sulfonate, concentrating the solution to obtain concentrated liquid with dry matter content of above 50% or spray drying to obtain powder, and concentrating the liquid or powder to obtain the fertilizer.
In the technical scheme of the product and the method, the plant raw material is one or more of bamboo, fungus grass, arundo donax, reed, crop straw, bagasse and coconut shell bamboo wood processing residues, and the crop straw is straw of wheat, rice, corn, soybean, sorghum and cotton. Preferably, the bamboo is phyllostachys pubescens or phyllostachys pubescens, particularly preferably, the bamboo is crushed bamboo.
In the preparation process of the fertilizer, the pulping process is a process of separating and depolymerizing the plant body and extracting and separating water-insoluble carbohydrate polymer-fiber material and water-soluble nutrient substances in the plant body, and the plant body is rich in various nutrient elements and biomass energy required by organisms. Therefore, the fertilizer produced by pulping by an acid method or an alkali method is the most reasonable application direction as a plant, animal and microorganism nutrition energy source. The fertilizer rich in high-concentration water-soluble biological organic matter components is the most suitable nutrient source for promoting ecological agriculture, regulating the acidity and alkalinity of soil and supplementing soil nutrients and organic matters, and the straw is the raw material capable of being recycled in a large amount. The application evaluation result shows that the fertilizer produced by the acid method or the alkali method slurry can be independently combined with each other or compounded with the nitrogen-phosphorus-potassium fertilizer to form a series of products with various functions of fertilizer retention and water retention, fertilizer supply and water absorption, overall balance nutrition, sand fixation and skinning, alkali binding and inhibition, complexation dissolution assistance, ecological restoration and the like, can be used as a series of biological nutrient sources of deserts, saline-alkali lands, fields, facility agriculture, gardens, acid-alkali soil conditioning, nutrient matrixes, edible fungus culture mediums and the like, and can be called as artificial mannose.
The invention also provides a novel acid method, a novel alkali method and a novel method for pulping by coupling raw materials of the acid method and the alkali method to produce the water-soluble fertilizer simultaneously, the method takes plant bodies, lime and sulfur dioxide as raw materials, potassium hydroxide or regenerated potassium hydroxide solution as an alkaline resolving agent and calcium bisulfide as active components and the acid resolving agent to carry out independent pulping, and the acid method and the alkali method are coupled to produce the pulp and the bio-based water-soluble fertilizer simultaneously respectively, and the method comprises the following steps: (1) Firstly pulping by a potassium hydroxide alkaline method, precipitating and recovering lignin or lignin and natural color pulp mixed slurry from a solution rich in high molecular lignin potassium by using sulfur dioxide, and recycling a potassium hydroxide aqueous solution by using double decomposition reaction of mixing potassium sulfite and slaked lime in a neutralization filtrate; (2) The precipitated and separated calcium sulfite solid is mixed with mechanically applied acid process slurry, and sulfur dioxide is continuously introduced to be converted into calcium bisulfide solution with excellent water solubility, and the calcium sulfite solution is used as an acid resolving agent to obtain high-quality natural color slurry with high yield, and a byproduct of the high-efficiency green calcium lignosulfonate water-soluble fertilizer or soil conditioner is obtained.
The invention uses sulfur dioxide to replace sulfuric acid or sulfuric acid aluminum acidation alkaline method slurry black liquor mixture, avoids the complex processes of gypsum generation, solid-liquid separation, washing, transportation and the like, uses only two cheap raw materials of sulfur dioxide and lime, can simultaneously skillfully develop two new processes of a potassium hydroxide method and a calcium bisulfide method to realize advantage complementation, opens up a new way for producing high-yield, high-quality unbleached pulp and high-added-value calcium lignosulfonate water-soluble fertilizer with low cost, and can produce and adjust the productivity of lignin potassium fertilizer and lignin sulfonate according to the requirement.
The novel acid method, alkaline method and acid method and alkaline method coupling co-production process for high yield and high quality unbleached pulp and bio-based water-soluble fertilizer are significant 'subversion' technological breakthroughs of key nodes of plant splitting and depolymerizing, grading and high quality full-value utilization. The great innovation results create a new way for producing the fertilizer by flexible pulping and create the most competitive industrial chain for pulping various raw materials and co-producing the water-soluble fertilizer bio-based efficient fertilizer.
In the technical scheme of the fertilizer product and the fertilizer production method, the plant raw materials are bamboo such as moso bamboo and green bamboo, dominant plants such as dominant grass, arundo donax, reed and the like, crop straws such as wheat, rice, corn, soybean, sorghum, cotton straw and the like, bagasse, coconut shell bamboo wood processing residues and the like. Preferably, the plant material is crushed bamboo, dominant fungus grass, arundo donax, straw, reed.
In the technical scheme of the product and the method, the sulfur dioxide is sulfur dioxide obtained by decomposing calcium sulfite, or sulfur dioxide is obtained by reducing desulfurized gypsum, phosphogypsum or fluorgypsum or natural gypsum at high temperature in a kiln, or the sulfur dioxide is obtained by burning or heating oxidation of sulfur, and the lime is lime obtained by decomposing calcium sulfite, or lime is obtained by reducing desulfurized gypsum, phosphogypsum or fluorgypsum or natural gypsum at high temperature in a kiln.
The sulfur dioxide and the sulfur dioxide in the calcium sulfite and the calcium bisulfide in the pulping process can be directly utilized as the raw materials of sulfur dioxide which is a byproduct in the sulfide ore smelting process, or the carbon high-temperature reduced gypsum in a kiln is used for simultaneously producing lime and steam and electricity, or the burning sulfur byproduct steam and electricity and other channels are used for obtaining the calcium-based raw materials, and slaked lime, carbide slag, cement, gypsum decomposers, preferably two decomposers which are the byproduct of the alkaline process and the byproduct of the calcium sulfite or the high-temperature of the flue gas desulfurization byproduct of the calcium sulfite or the calcium sulfate, can promote the recycling of three wastes, so that the low-cost and large-scale production of organisms and products is more guaranteed as the raw materials.
In the pulping method, the solid-to-liquid ratio of the folded solid weight of the plant raw material to the calcium bisulfate solution is 1:3-8. Preferably, in the alkaline pulping process, the addition amount of the calcium hydroxide is about 3.5% of the weight of the folded plant raw material; preferably, in the acid pulping process, the added amount of the calcium bisulfate is about 10% of the weight of the folded plant raw material.
In the pulping method, the auxiliary agent, preferably aluminum sulfate, can be added in the process of kneading, pulp extrusion and/or pulping after the steaming and boiling and/or before the pulping separation; the addition amount of aluminum sulfate can be 0.5-30% of the weight of the fiber. The potassium-method slurry or the calcium sulfite-method slurry can be reused for many times after the separating agent and the washing water are supplemented until the solution is saturated, and a small part of concentrated solution can be extracted from most of the side line of the solution to save energy and reduce consumption to the greatest extent and reduce cost.
The other scheme of the invention is that lime, plant ash, potassium sulfite, flue gas desulfurization byproducts such as calcium sulfite, sulfur dioxide and the like which are low in cost and easy to obtain are used as raw materials, calcium bisulfide is used as an active component, and an acid process and an alkali process are coupled to prepare two kinds of pulp and a co-production process of the two bio-based water-soluble fertilizers respectively.
Specifically, the invention also provides a process for co-producing the two bio-based water-soluble fertilizers, which comprises the following steps:
according to the solid-to-liquid ratio of the absolute dry mass of the plant material to the calcium bisulfate solution of 1:3-10, the dosage of the calcium bisulfate in the calcium bisulfate solution is 5-15% of the absolute dry mass of the plant material, the pH value of the calcium bisulfate solution is regulated to 1-5 by sulfuric acid or sulfuric acid solution, the soaking and steaming temperature is 80-130 ℃, the soaking and steaming time is 2-6 hours, kneading, pulping, filtering and washing are carried out to obtain the unbleached pulp, the filtered filtrate is red liquid taking calcium lignosulfonate as a main component, the red liquid is supplemented with the calcium bisulfate and circularly used after regulating the pH value, the solution can be partially or completely extracted after being circularly used to nearly saturation, the pH value of the solution is regulated to 6-8, and the solution can be directly diluted for use or concentrated into liquid with the solid content of more than 50% or spray dried into powder, namely the water-soluble fertilizer taking the calcium lignosulfonate as the main component; or adding potassium sulfate or ammonium sulfate into the solution with the pH value regulated to 6-8 according to the required proportion, separating out precipitated calcium sulfate to obtain a solution meeting the requirement of the content of potassium lignin sulfonate or ammonium lignin sulfonate, and directly diluting the solution to be used as a potassium lignin or ammonium lignin fertilizer, or concentrating the solution to be concentrated liquid with the dry matter weight content of more than 50% or spray-drying the concentrated liquid to obtain powder of the bio-based sulfonate, thus obtaining the potassium lignin or ammonium lignin product.
According to the use requirement, the alkaline black liquor taking potassium lignin as a main component or the acid red liquor taking calcium lignin sulfonate as a main component, which is extracted by the method, can be directly diluted or acidified according to local conditions, or the black liquor and the red liquor are compounded for use, the black liquor and the red liquor can be concentrated and spray-dried to prepare a liquid fertilizer or a water-soluble solid fertilizer product, and the liquid fertilizer or the water-soluble solid fertilizer product can be compounded with slurry, biomass, organic fertilizer and fertilizer singly or jointly to form a paper film fertilizer, a nutrient substrate, an edible fungus culture medium, a slow-release fertilizer, a water-soluble fertilizer, a biological organic fertilizer and a foliar fertilizer; can be used as a soil conditioner for acid-base neutralization and organic matter and medium trace element supplementation of acid soil, alkaline soil or normal soil.
The beneficial effects of the invention are that
The slurry is rich in water-soluble nutrient components such as lignin and biological nutrient elements such as calcium, potassium, nitrogen and phosphorus, is an ideal biological nutrient source and biological energy source, and can be used as main functional components of water-soluble fertilizer, paper-based mulching film, biological matrix culture medium, foliar and root fertilization and soil conditioner. The invention can use circulating feed liquid with lower concentration (1-2.5%) of calcium bisulfate and potassium hydroxide (1-3.5%), respectively and independently pulp or pulp and mix pulp for papermaking in a coupling way under the conditions of lower soaking and steaming temperature (80-130 ℃) and shorter time (1-3), and coproduce water-soluble fertilizers and soil conditioners such as calcium lignosulfonate or potassium lignosulfonate with good service performance, thereby realizing the full-price utilization of plants and all pulping raw materials, greatly reducing the energy consumption, material consumption and water consumption of pulping, generating no secondary pollution, producing high-quality local paste and water-soluble biological base fertilizers and soil conditioners with good service performance in a high-efficiency, simple and convenient and large-scale manner, and being widely used for desert and land ecological restoration such as deserts, saline-alkali lands, soil conditioning of fields and greenhouses, high-standard farmland construction and crop yield improvement.
The fertilizer and the preparation process of the fertilizer can fully and efficiently utilize biomass resources such as crop straws, bamboo, reed, dominant bacteria and grass, overcome the defects of serious pest and disease damage, low utilization rate, difficult degradation, serious emission of greenhouse gases such as methane and the like existing in straw returning, promote sulfide ore processing and utilization of industrial byproducts or mineral resources such as sulfur dioxide, gypsum and the like, and the produced fertilizer is highly rich in nutrient components such as potassium, sulfonated lignin, calcium element and the like which are beneficial to crop growth.
The invention solves the problem of low efficiency of pulping black liquor or red liquor as fertilizer in China, develops low production cost, does not have secondary pollution, and can realize full utilization of a large amount of pulping liquor resources. Can promote the effective utilization of raw materials such as moso bamboo, straw, industrial byproduct gypsum and the like, and opens up a new way for the construction of ecological restoration and ecological industry group and the split, depolymerization and grading utilization of biomass to create a bio-based industry chain.
Drawings
FIG. 1 is a diagram of a biobased industrial chain and an ecological overnight cyclic economy.
Detailed Description
The technical scheme of the invention is further described below by combining specific embodiments. These examples are only for illustrating the present invention and are not intended to limit the scope of the present invention.
Example 1: basic nutrient characteristics of potassium lignin powder fertilizer and calcium lignin sulfonate powder fertilizer
Basic nutrients were measured by the NY525-2012 and GBT18877-2020 standards, allThe content of The Organic Carbon (TOC) is measured by adopting a potassium dichromate-sulfuric acid oxidation method, and the content of Total Nitrogen (TN) is measured by adopting H 2 SO 4 -H 2 O 2 The Total Phosphorus (TP) content is determined by a digestion-semi-trace Kjeldahl nitrogen determination method and adopts H 2 SO 4 -H 2 O 2 The total potassium (TK) content is determined by adopting a digestion-molybdenum-antimony colorimetric method by adopting H 2 SO 4 -H 2 O 2 Digestion-flame photometry; the heavy metal elements are measured by an ICP inductively coupled plasma spectrometer (comprising As, cd, cr, pb), and the results are as follows:
TABLE 1 analysis results of basic nutrients of lignin potash fertilizer and calcium lignosulfonate powder fertilizer
TABLE 2 content of heavy metal elements in Potassium Lignin fertilizer and calcium Lignosulfonate powder fertilizer
As shown in Table 1, the potassium lignin powder fertilizer and the calcium lignin sulfonate powder fertilizer have higher organic matter content, and the organic matter nutrient is far higher than the agricultural and national standards. The lignin potassium powder fertilizer is a high-potassium fertilizer, and simultaneously, the two fertilizers can be compounded or mixed with nitrogen, phosphorus and potassium nutrients in advance during actual application to form the multi-effect fertilizer. As shown in Table 2, the heavy metal content of the potassium lignin powder fertilizer and the calcium lignin sulfonate powder fertilizer is far lower than that required in agriculture and national standards, and the safety and harmlessness of the products are proved.
Example 2: evaluation of tolerance of seeds to alkaline pulping black liquor fertilizer and acid pulping red liquor fertilizer
GI (germination index) is one of the effective indicators for checking fertilizer toxicity, by which the applied concentration can be initially determined. According to the experiment, cabbage seeds are used, 5ml of lignin potassium fertilizer and lignin calcium sulfonate fertilizer solutions with different dilution concentration gradients are respectively used, 20 seeds are added into a culture dish, germination and seed tolerance evaluation experiments are carried out, and the results are as follows:
TABLE 3 germination tolerance of lignin potash fertilizer and lignin calcium sulfonate fertilizer seeds
As can be seen from Table 3, the lignin potash fertilizer concentration was 0.6%, the calcium lignosulfonate fertilizer concentration was 1.0% and was substantially non-toxic to seed development, whereas the lignin potash fertilizer and the calcium lignosulfonate fertilizer were diluted to 0.3% and were completely non-toxic to seed development.
Example 3: influence of different application amounts of black liquid fertilizer and red liquid fertilizer on soil pH and EC
Test one, according to the preparation method of the lignin potash fertilizer of the patent, the lignin potash fertilizer is prepared, and then three different concentration gradients of 1%,0.6% and 0.3% are diluted, and the pH value and the EC value of the lignin potash fertilizer are respectively tested so as to ensure the optimal fertilizer concentration in the field. And (3) mixing the lignin potash fertilizer into acid soil with pH of 4.21 according to the folding and fixing amount, and observing the pH effect of the lignin potash fertilizer on the soil and the influence on the EC value.
TABLE 4 EC content of lignin Potassium fertilizer and calcium Lignosulfonate fertilizer at different concentrations
The standard EC value of the traditional water-soluble fertilizer application is 1-4mS/cm, and Table 4 shows that the lignin potash fertilizer and the lignin calcium sulfonate fertilizer completely meet the traditional water-soluble fertilizer application standard when the content of the lignin potash fertilizer and the lignin calcium sulfonate fertilizer is below 0.6%.
Table 5 evaluation of lignin potash fertilizer soil conditioning
| Numbering device | Concentration of application | pH | EC(mS/cm) |
| 4-7 | H2O(CK) | 4.21 | 0.11 |
| 4-8 | 1kg of soil is added with 2g of lignin potash fertilizer | 4.30 | 0.16 |
| 4-9 | 1kg of soil is added with 5g of lignin potassium fertilizer | 4.40 | 0.18 |
| 4-10 | 1kg of soil is added with 10g of lignin potash fertilizer | 4.82 | 0.27 |
The results in Table 5 show that the lignin potash fertilizer has an improvement effect on acid soil. The pH value is improved by 14% compared with the control when the adding amount is 10g/kg of soil; when the addition amount is 5g/kg of soil, the pH is 4.5% higher than that of the control; the pH value of the soil with the addition of 2g/kg is 2% higher than that of the control soil, and researches show that the EC value of the soil suitable for the growth of most crops is in the range of 0.2-0.6mS/cm, the salt index of the saline soil and the relation between the salt index and the chemical composition are mentioned, the EC value is lower than 0.37mS/cm, the saline soil belongs to non-saline soil, and the tabular data show that the EC value is increased but is in the safe value range for the growth of the crops. Both fertilizers simultaneously provide bio-based nutrients to the soil.
Example 4: calcium lignosulfonate fertilizer and lignin potash fertilizer for pepper planting effect
Experiment one, experiment was carried out in 2021, lignin potash fertilizer was prepared according to the preparation method of lignin potash fertilizer of this patent, lignin calcium sulfonate was prepared according to the preparation method of lignin calcium sulfonate of this patent, lignin potash fertilizer and lignin calcium sulfonate were applied to pepper planting, the species selection spring was ground huge dragon, the place was located S302 in the southern Pingjie county and the city, the vegetable was planted in a concentrated manner, and the cell area was 20m 2 The random granule arrangement is processed, and each process is as follows:
CK: organic bacterial fertilizer and conventional fertilizer (N-15:P) 2 O 5 -15∶K 2 O-15)
T1: organic bacterial fertilizer and lignin potash fertilizer 40 kg/mu (folded solid) +conventional fertilizer with reduced application (base fertilizer, additional fertilizer and reduced application 30%)
T2: organic bacterial fertilizer and calcium lignosulfonate fertilizer 40 kg/mu (folded solid) +conventional fertilizer with reduced application (base fertilizer, additional fertilizer and 30%)
TABLE 6 influence of calcium Lignosulfonate and Lignosussic fertilizers on the growth vigor of Capsicum annuum
As shown in Table 6, the heights of T1 and T2 are 6.37% and 1.79% higher than CK, the fruit bearing number of T1 is 7.10% higher than CK, and the main stem length of T2 is 8.10% higher than CK.
TABLE 7 influence of calcium Lignosulfonate and Lignosussic Potassium fertilizers on Capsici fructus quality
| Numbering device | Weight per gram of single fruit | Single fruit length/cm | Single fruit width/mm | Fruit hardness/kg | Soluble solids% |
| CK | 33.86 | 31.25 | 17.31 | 3.59 | 3.77 |
| T1 | 36.99 | 33.67 | 18.43 | 3.56 | 3.97 |
| T2 | 25.10 | 29.50 | 16.44 | 3.66 | 4.07 |
The results in Table 7 show that the weight of the single fruit is highest in T1 treatment, T1 is increased by 9.24% compared with the control, and the length and width of the single fruit are one of the morphological indexes of the capsicum, wherein the length and width of the single fruit of T1 are obviously increased by 7.74 and 6.47% compared with the control. The indexes of T1 and T2 are improved by 5.31 percent and 7.96 percent compared with the indexes of CK soluble solids.
Table 8 influence of calcium Lignosulfonate and Lignosussic fertilizers on Capsici organic acids
| Fertilizer | Organic acid of capsicum (%) |
| CK | 0.2 |
| T1 | 0.248 |
| T2 | 0.44 |
After the calcium lignosulfonate fertilizer and the potassium lignosulfonate fertilizer are added to improve soil, the accumulation of organic acids in the capsicum is promoted, T2 is 2.2 times of CK treatment, and T1 is improved by 24% relative to CK.
TABLE 9 influence of calcium Lignosulfonate and Potassium Lignosulfate on soil pH, EC and temperature
As shown in Table 9, the effect of promoting the pH value of soil after adding lignin potash fertilizer is obvious, and the effect is improved by 6.70% compared with CK.
Table 10 influence of calcium Lignosulfonate and Lignosussic Potassium fertilizers on soil nutrient
| Numbering device | G/kg of organic matter | Total nitrogen g/kg | Alkaline hydrolysis of nitrogen mg/kg | Quick-acting phosphorus mg/kg | Quick-acting potassium mg/kg |
| CK | 45.76 | 0.34 | 5.59 | 7.30 | 108.50 |
| T1 | 49.86 | 0.39 | 7.38 | 3.63 | 36.91 |
| T2 | 49.14 | 0.40 | 7.54 | 8.68 | 112.90 |
As shown in Table 10, the content of T1 treated organic matter is obviously increased, wherein T1 and T2 are respectively increased by 8.86 percent and 7.39 percent compared with CK organic matter, total nitrogen is increased by 14.71 percent and 17.65 percent, and alkaline hydrolysis nitrogen is increased by 32.02 percent and 34.88 percent. The T2 treatment has 18.90% and 4.06% higher quick-acting phosphorus and quick-acting potassium than the control. The data show that the lignin potash fertilizer and the lignin calcium sulfonate fertilizer have remarkable promotion effect on soil nutrient accumulation.
Table 11 influence of calcium Lignosulfonate and Lignosussic Potassium fertilizers on the bacterial count in soil
| Numbering device | Bacteria cfu/g |
| CK | 6.93×10 5 |
| T1 | 1.48×10 6 |
| T2 | 7.35×10 5 |
Table 11 shows that the concentration of T1 bacteria was 2.14 times that of CK and that of T2 was 1.06 times that of CK.
Table 12 Effect of calcium Lignosulfonate and Lignosussic Potassium fertilizers on Capsici fructus yield
As shown in table 12, after picking peppers throughout the growth period, each treatment was found to be higher than the control, with T1, T2 significantly higher than control 18.64% by accurate weighing.
Experiment II, applying calcium lignosulfonate and potassium lignosulfonate to pepper cultivation soil, selecting Chun-Mei-long, and placing in S302 channels of Nanzhong city and county, vegetable concentrated planting land and 20m of district area 2 A random granule arrangement is processed. The treatment comprises the following steps:
CK: conventional fertilizer and organic bacterial fertilizer
T1: 60 kg/mu of lignin potash fertilizer, 40 kg/mu of calcium lignosulfonate fertilizer and 30% of conventional fertilizer
TABLE 13 influence of different treatments on the growth vigor of Capsici fructus
As shown in Table 13, T1 was increased by 5.26% relative to the CK plant height, the stem thickness was increased by 12.14%, and the fruit setting number was increased by 21.15%. The compound application of the calcium lignosulfonate fertilizer and the potassium lignosulfonate fertilizer has the effect of promoting the growth vigor of crops.
TABLE 14 Effect of different treatments on Capsici fructus quality
| Numbering device | Weight per gram of single fruit | Single fruit length/cm | Single fruit width/mm | Fruit hardness/kg | Soluble solids% |
| CK | 18.87 | 23.37 | 15.67 | 3.20 | 3.93 |
| T1 | 18.00 | 22.75 | 16.45 | 4.53 | 4.33 |
As shown in Table 14, the hardness of T1 fruit was increased by 41.56% relative to CK, and the soluble solids were increased by 10.18%.
TABLE 15 influence of different treatments on capsicum soil
| Numbering device | Soil temperature (. Degree. C.) | Soil moisture content (%) | Soil pH | Soil EC (uS/cm) |
| CK | 21.65 | 10.95 | 6.08 | 215.50 |
| T1 | 22.15 | 12.83 | 5.74 | 319.50 |
As shown in Table 15, the temperature and the water content of the T1 soil are higher than CK, the EC content of the soil is higher than EC 48.26%, and the fact that the calcium lignosulfonate and the potassium lignosulfonate are used in combination can promote the heat preservation and the water retention of the soil and promote the nutrient accumulation.
Table 16 effects of different treatments on pepper soil nutrients
| Numbering device | Alkaline hydrolysis of nitrogen mg/kg | Quick-acting phosphorus mg/kg | Quick-acting potassium mg/kg |
| CK | 5.96 | 5.6 | 36.02 |
| T1 | 7.32 | 7.57 | 57.18 |
As shown in Table 16, the alkaline hydrolysis nitrogen, the available phosphorus and the available potassium in T1 are all higher than the control, which indicates that the mixed use of the calcium lignosulfonate and the lignin potassium fertilizer can promote the dissolution of nutrients, form rich plant available nutrients and further promote the growth of the capsicum.
Example 5: effect of calcium lignosulfonate and potassium lignosulfonate on soil bacterial concentration
The lignin potash fertilizer is prepared according to the preparation method of the lignin potash fertilizer, and the calcium lignin sulfonate fertilizer is prepared according to the preparation method of the calcium lignin sulfonate fertilizer. The lignin potash fertilizer and the lignin calcium sulfonate fertilizer are respectively applied into flowerpots filled with 800g of soil at the application amount of 10 kg/mu, 20 kg/mu, 40 kg/mu and 60 kg/mu, and the bacterial count is measured through stage culture. The test treatment is as follows:
CK: no fertilizer
Ca-10:10 kg/mu lignin calcium fertilizer
Ca-20:20 kg/mu lignin calcium fertilizer
Ca-40:40 kg/mu lignin calcium fertilizer
Ca-60:60 kg/mu lignin calcium fertilizer
K-10:10 kg/mu lignin potash fertilizer
K-20:20 kg/mu lignin potash fertilizer
K-40:40 kg/mu lignin potash fertilizer
K-60:60 kg/mu lignin potash fertilizer
TABLE 17 bacterial count for each treatment
| Numbering device | Bacteria cfu/g |
| CK | 7.50×10 5 |
| Ca-10 | 5.15×10 6 |
| Ca-20 | 1.60×10 7 |
| Ca-40 | 1.30×10 7 |
| Ca-60 | 1.89×10 7 |
| K-10 | 5.40×10 5 |
| K-20 | 2.41×10 6 |
| K-40 | 8.35×10 6 |
| K-60 | 1.31×10 7 |
From the test results of Table 17, it was revealed that as the applied amount of the calcium lignosulfonate and the potassium lignosulfonate increased, the bacterial concentration increased, wherein the applied amount of 60 kg/mu of the calcium lignosulfonate was 25.2 times as much as that of CK, and the applied amount of 60 kg/mu of the potassium lignosulfonate was 17.47 times as much as that of CK.
Example 6: application of calcium lignosulfonate fertilizer in saline-alkali soil silage corn planting
The calcium lignosulfonate fertilizer produced by the method is subjected to silage corn fertigation test evaluation. The test verifies the influence of 25% and 50% of fertilizer application reduction on silage corn quality by applying calcium lignosulfonate fertilizer. The treatment is as follows:
CK: conventional fertilization (N-25:P) 2 O 5 -10∶K 2 O-0)
T1: calcium lignosulfonate fertilizer 40 kg/mu + 25% of fertilizer
T2: 40 kg/mu of calcium lignosulfonate plus reduced fertilizer 50%
Table 18 Effect of different fertilizer concentrations on corn yield after application of calcium Lignosulfonate fertilizer
| Numbering device | kg/667m 2 | Yield increase relative to CK |
| CK | 4980 | / |
| T1 | 7870 | 58.03％ |
| T2 | 7150 | 43.57％ |
The data in table 18 shows that after applying the calcium lignosulfonate fertilizer, both T1 and T2 yields increased significantly, wherein T1 increased 58.03% relative to CK and T2 increased 43.57% relative to CK.
TABLE 19 influence of different fertilizer concentrations applied reduction on corn quality after application of calcium lignosulfonate
The data in table 19 shows that the application of calcium lignosulfonate fertilizer and the reduction of 25% of fertilizer (T1) dry matter content increased by 8.26% and the reduction of 50% of fertilizer (T2) dry matter content increased by 0.87% compared to conventional fertilization. The crude protein content, T1 is 0.26% higher than traditional fertilization, and T2 is 2.23% higher than traditional fertilization. The soluble carbohydrate content of T2 is improved by 11.96% compared with the traditional fertilization. The method shows that the calcium lignosulfonate water-soluble fertilizer co-produced by the acid pulping method has a great improvement effect on the yield and quality of silage corns.
Table 20 Effect of different applied fertilizer concentration soil nutrient after application of calcium Lignosulfonate
| Nutrient index | CK | T1 | T2 |
| pH | 8.11 | 8.26 | 8.16 |
| Conductivity (mS/cm) | 0.55 | 0.34 | 0.38 |
| Organic matter (g/kg) | 19.00 | 18.00 | 19.50 |
| Total nitrogen (g/kg) | 0.88 | 0.86 | 0.86 |
| Whole phosphorus (g/kg) | 0.97 | 1.09 | 0.99 |
| Whole potassium (g/kg) | 23.10 | 23.10 | 22.40 |
| Quick-acting potassium (mg/kg) | 171.00 | 182.00 | 182.00 |
| Available phosphorus (mg/kg) | 13.10 | 22.50 | 29.70 |
| Hydrolytic nitrogen (mg/kg) | 61.60 | 53.60 | 62.30 |
The data in Table 20 shows that after applying the fertilizer, the conductivity is reduced relative to the control, and the content of available phosphorus and the content of available potassium are increased, wherein the content of available potassium is increased by 6.42%, and the content of available phosphorus T1 and T2 is increased by 71.76% and 126.72% relative to T1.
Example 7: single and compound nutrient of calcium lignosulfonate and influence of potassium lignin on tea planting
The test takes the variety of Huangguanyin 105 tea tree as a research object to research the quality and yield of soil and tea respectively, and simultaneously, the compound performance of the calcium lignosulfonate fertilizer is verified based on the compound ammonium sulfate of the calcium lignosulfonate fertilizer. The tested fertilizer is gold and silver bead blended fertilizer-amino acid BB fertilizer (N14%, P6%, K10%, organic matter 10%, amino acid 6%), ammonium sulfate (nitrogen content is more than or equal to 21%), lignin potassium fertilizer and lignin calcium sulfonate fertilizer.
The test treatment is as follows:
CK: gold and silver bead blended fertilizer-amino acid BB fertilizer 42.6 kg/mu
T1: calcium lignosulfonate fertilizer 40 kg/mu+ammonium sulfate 2.5 kg/mu
T2: 20 kg/mu of calcium lignosulfonate plus 1.25 kg/mu of ammonium sulfate plus less applied gold and silver bead blended fertilizer-amino acid BB fertilizer 30% (29.82 kg/mu)
T3: lignin potash fertilizer 40 kg/mu + reduced application gold and silver bead blended fertilizer-amino acid BB fertilizer 30% (29.82 kg/mu)
Table 21 physical and chemical influence of lignin Potassium fertilizer and calcium Lignosulfonate fertilizer on tea planting soil
As shown in Table 21, the lignin potash fertilizer and the lignin calcium sulfonate fertilizer both have promotion effect on soil organic matters, T3 treatment is most remarkable, and the promotion rate is 17.54% compared with control, and T1 and T2 are respectively 11.90% and 7.78% compared with control organic matters. The total nitrogen content, alkaline hydrolysis nitrogen content, quick-acting phosphorus content and quick-acting potassium content of the test group are lower than those of the control, and the calcium lignosulfonate fertilizer and the lignin potassium fertilizer of the test group can promote the absorption and utilization of crop nutrients, so that the yield is improved, and the content of residual nitrogen, phosphorus and potassium in soil is reduced.
Table 22 influence of Potassium lignin fertilizer and calcium Lignosulfonate fertilizer on tea quality
As shown in Table 22, the introduction of lignin potash fertilizer promoted tea quality improvement, wherein dry matter, tea polyphenols, flavones, water extract, caffeine were all higher than control, wherein T3 tea polyphenols were 18.52% higher than CK and flavones were 27.33% higher than CK. Under the condition of 100% fertilizer reduction and only calcium lignosulfonate fertilizer application, the quality of the T1 is higher than that of the control except for caffeine, which indicates that the quality of the tea can be improved under the single action of the calcium lignosulfonate fertilizer.
Table 23 influence of Potassium lignin fertilizer and calcium Lignosulfonate fertilizer on soil microbial quantity
| Numbering device | Bacteria cfu/g |
| CK | 1.26×10 5 |
| T1 | 2.71×10 5 |
| T2 | 3.40×10 5 |
| T3 | 2.35×10 5 |
As shown in Table 23, the numbers of T1, T2, and T3 treated bacteria were all higher than the control.
Table 24 influence of Potassium lignin fertilizer and calcium Lignosulfonate fertilizer on tea yield
As shown in Table 24, both the calcium lignosulfonate fertilizer and the ammonium sulfate compound fertilizer and the potassium lignosulfonate fertilizer promote the yield to be improved, and the T2 is most obvious and increases 36.29 percent compared with the CK. The yield can be increased by 20.88% still without applying traditional gold and silver bead fertilizer by 40 kg/mu of calcium lignosulfonate fertilizer.
Example 8: influence of calcium lignosulfonate fertilizer on bamboo planting
The test uses moso bamboo as a research object, and the tested compound fertilizer (special for bamboo) is a commercially available moso bamboo applicable compound fertilizer, and the total nutrient is 25% (N: P: K=14: 2: 9) and contains microelements such as rare earth and silicon. The calcium lignosulfonate fertilizer is prepared by the preparation method of the calcium lignosulfonate fertilizer of the patent. The test treatments are shown in Table 25 below.
Table 25 test treatment
| Sample plot | Compound fertilizer/kg | Calcium lignosulfonate fertilizer/kg |
| CK1 | 0.00 | 0.00 |
| CK2 | 3.00 | 0.00 |
| T1 | 1.50 | 1.50 |
| T2 | 0.75 | 2.25 |
| T3 | 2.25 | 0.75 |
| T4 | 0.00 | 3.00 |
Influence of Table 26 calcium Lignosulfonate fertilizer on moisture content of bamboo forest soil
As in Table 26The water content data shows that with the increase of the application amount of the calcium lignosulfonate, the water content of the soil and the maximum water yield are gradually increased, which proves that the calcium lignosulfonate has obvious promotion effect on the water retention capacity of the soil. The water content of the soil of T4 is highest, the water holding capacity of the soil is greatest, and the water content and the water holding capacity of the soil layer of 0-20cm are obviously higher than those of the soil layer treated by 18.15 percent and 68.21 percent.
Table 27 influence of calcium Lignosulfonate fertilizer on physical Properties of bamboo forest soil
The data in table 27 show that calcium lignosulfonate will promote a decrease in soil volume weight and increase the total porosity of the soil, wherein T1 soil volume weight is reduced by 18.28% as compared to CK1 and total porosity is increased by 60%. The analysis of the data shows that the calcium lignosulfonate fertilizer has remarkable promotion effect on the physical properties of soil and the effect is most remarkable in a soil layer of 0-20 cm.
Influence of Table 28 calcium Lignosulfonate fertilizer on soil nutrient of bamboo forest
The data in Table 28 shows that the application of the calcium lignosulfonate has a remarkable promoting effect on the nutrients of the soil cultivated in the bamboo forests, and the application effect of the calcium lignosulfonate is verified and the dosage is optimized in the test. 1.5kg of calcium lignosulfonate and 1.5kg of compound fertilizer (T1) have the most obvious effect on soil nutrients, wherein the total nitrogen is increased by 88.24% in a soil layer of 0-20cm compared with the total nitrogen which is not applied with fertilizer (CK 1), and is increased by 106.45% compared with the total nitrogen which is applied with fertilizer (CK 2) singly; the total phosphorus is improved by 31.03% in a soil layer of 0-20cm compared with CK1, and is improved by 50% in a soil layer of 20-40 cm; the total potassium is 15.15% higher than CK1 in a soil layer of 0-20cm, and 14.44% higher than CK 2; the quick-acting phosphorus is improved most obviously, 97.07 is improved in a soil layer of 0-20cm relative to CK1, and 194.38 percent is improved relative to CK 2. Analysis of comprehensive nutrient data shows that after the compound fertilizer and the calcium lignosulfonate fertilizer are compounded in a ratio of 1:1, the compound fertilizer has remarkable promotion effect on soil layers of 0-60cm of phyllostachys pubescens cultivation soil.
Claims (7)
1. A method for preparing pulp and co-producing water-soluble fertilizer by coupling novel acid method, novel alkali method and acid method and alkali method raw materials, wherein the method uses plant raw materials, slaked lime and sulfur dioxide as raw materials, potassium hydroxide or regenerated potassium hydroxide solution as an alkaline resolving agent and calcium bisulfide as an active component and an acid resolving agent to independently prepare pulp and co-produce bio-based water-soluble fertilizer by coupling the acid method and the alkali method, and the method comprises the following steps:
(1) Firstly pulping by a potassium hydroxide alkaline method, then precipitating and recovering lignin or lignin and natural color pulp mixed slurry from a solution rich in high molecular lignin potassium by using sulfur dioxide or sulfurous acid solution, then carrying out mixed double decomposition reaction on the neutralization filtrate and slaked lime to regenerate a potassium hydroxide aqueous solution, and recycling the potassium hydroxide aqueous solution to pulping by the alkaline method;
(2) Mixing the precipitated and separated calcium sulfite solid with mechanically applied acid pulping liquid, continuously introducing sulfur dioxide or adding a sulfurous acid solution to convert into a calcium bisulfide solution with excellent water solubility, and using the calcium sulfite solution as an acid resolving agent in the acid pulping to obtain high-quality natural color pulp with high yield, and simultaneously preparing a byproduct of calcium lignosulfonate water-soluble fertilizer or a soil conditioner, wherein the acid pulping is a pulping method by using the sulfuric acid-containing calcium bisulfide solution as the resolving agent;
Wherein, the method for co-producing the water-soluble fertilizer is selected from the following steps:
the acid method for co-producing the calcium-based water-soluble fertilizer comprises the following steps: according to the solid-to-liquid ratio of the mass of the absolute dry plant raw material to the calcium bisulfate solution of 1:3-10, the dosage of the calcium bisulfate in the calcium bisulfate solution is 5-15% of the mass of the absolute dry plant, the pH value of the calcium bisulfate solution is regulated to 1-5 by sulfuric acid, the soaking and steaming temperature is 80-130 ℃ and steaming time is 2-6 hours, the conventional pulping method is used for kneading, pulping, filtering, washing, filtering filtrate to obtain red liquid with calcium lignosulfonate as a main component, the red liquid is circularly used after supplementing the calcium bisulfate and regulating the pH value, the pH value of the solution is regulated to 6-8 after circularly used until saturation, and the solution is directly diluted or concentrated into a liquid product with the solid content of more than 50% or a powder product with the calcium lignosulfonate as the main component after spray drying; or proportioning potassium sulfate or ammonium sulfate according to the requirement, separating out precipitated calcium sulfate to obtain a solution meeting the requirement of potassium lignosulfonate or ammonium lignosulfonate content, and directly diluting or concentrating the solution to a concentrated liquid with the dry matter weight content of more than 50% or spray drying the concentrated liquid to obtain a biobased sulfonate series powder water-soluble fertilizer product; or alternatively
The coupling process of the alkaline method and the acid method comprises the following steps: kneading, pulping, filtering and washing filtrate which is prepared by a conventional pulping method and contains lignin potassium as a main component according to the mass of the absolute dry plant material and the solid-liquid ratio of potassium hydroxide solution of 1:3-10, wherein the dosage of potassium hydroxide is 10-15% of the mass of the absolute dry plant material, the concentration of potassium hydroxide is 3%, the soaking and steaming temperature is 80-130 ℃ and the steaming time is 0.5-6h, supplementing potassium hydroxide to circularly apply until saturation, controlling the pH value of the solution to be below 10, and directly diluting or concentrating the solution into liquid with the solid content of more than 50% or spray drying the solution into powder to obtain the acid soil conditioner and the bio-based water-soluble fertilizer which contain the lignin potassium as the main component; soaking, steaming and boiling with potassium hydroxide, kneading, pulping, introducing sulfur dioxide into the separated black liquor or adding sulfur dioxide aqueous solution to acidify to pH 8-9, heating to 160 ℃ for 2-3 hours to carry out sulfonation reaction, and synthesizing potassium lignin sulfonate to be used as a liquid fertilizer.
2. The method of claim 1, wherein the co-production of the bio-based calcium sulfonate water-soluble fertilizer, the bio-based calcium sulfonate water-soluble fertilizer produced by the acid process and the lignin potassium water-soluble fertilizer co-produced by the alkali process are used independently, in combination with each other or in combination with the nitrogen-phosphorus-potassium fertilizer.
3. The method according to claim 1 or 2, characterized in that the water-soluble fertilizer co-produced by an alkaline process and an acid process is used for producing one or more products of humic acid fertilizer, macroelement fertilizer, secondary element fertilizer and trace element fertilizer in a compatible manner; in the water-soluble fertilizer or compound fertilizer product, the weight percentage of organic matters is 40% -96% of the dry weight of the fertilizer, the weight percentage of total nitrogen is 0.3% -5.0% of the dry weight of the fertilizer, the weight percentage of phosphorus in terms of phosphorus pentoxide is 0.1% -5.0% of the dry weight of the fertilizer, the weight percentage of potassium in terms of potassium oxide is 0.5% -15.0% of the dry weight of the fertilizer, the weight percentage of calcium ions is 0.5% -15% of the dry weight of the fertilizer, and the weight percentage of sulfur elements is 0.5% -10% of the dry weight of the fertilizer.
4. The fertilizer prepared according to any one of claims 1-3, wherein the organic matters in the fertilizer are more than or equal to 60% by weight of the dry weight of the fertilizer, the total nitrogen is more than or equal to 0.3% by weight of the dry weight of the fertilizer, the phosphorus is more than or equal to 0.1% by weight of the dry weight of the fertilizer calculated by phosphorus pentoxide, the potassium is more than or equal to 1% by weight of the dry weight of the fertilizer, the calcium ions are more than or equal to 1% by weight of the dry weight of the fertilizer, and the sulfur elements are more than or equal to 1% by weight of the dry weight of the fertilizer.
5. The fertilizer of claim 4, wherein the organic matter weight in the fertilizer is 60% -96% by weight of the dry weight of the fertilizer, the total nitrogen weight is 0.3% -0.5% by weight of the dry weight of the fertilizer, the phosphorus is 0.1% -0.6% by weight of the dry weight of the fertilizer calculated by phosphorus pentoxide, the potassium is 1% -15% by weight of the dry weight of the fertilizer calculated by potassium oxide, the calcium ion weight is 1% -10% by weight of the dry weight of the fertilizer, and the elemental sulfur weight is 1% -10% by weight of the dry weight of the fertilizer.
6. The fertilizer of claim 4, wherein the fertilizer comprises 60-70% by weight of organic matter based on dry weight of the fertilizer, 9-15% by weight of potassium based on dry weight of the fertilizer, and potassium lignin.
7. The fertilizer according to claim 4 or 5, wherein the organic matters in the fertilizer are 60% -96% by weight of the dry weight of the fertilizer, the sulfur element is 1% -10% by weight of the dry weight of the fertilizer, the fertilizer contains calcium lignosulfonate, and the calcium ions are 1% -10% by weight of the dry weight of the fertilizer.
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| GB723412A (en) * | 1949-06-01 | 1955-02-09 | Inst Internat Financier | Improvements relating to methods of treating the waste liquors obtained in the decomposition of lignified cellulose-containing materials |
| FR1173329A (en) * | 1957-03-25 | 1959-02-24 | Crown Zellerbach Corp | Manufacture of dimethyl sulfide from pulp mill waste liquors |
| US2906659A (en) * | 1953-07-13 | 1959-09-29 | Abitibi Power & Paper Co | High yields bisulphite pulping process |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US9090915B2 (en) * | 2008-04-22 | 2015-07-28 | Wisconsin Alumni Research Foundation | Sulfite pretreatment for biorefining biomass |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB269909A (en) * | 1926-04-21 | 1928-07-19 | Pierre Alfred Barbou | Improvements in or relating to treating residual liquors accruing from the treatment of cellulose material |
| GB723412A (en) * | 1949-06-01 | 1955-02-09 | Inst Internat Financier | Improvements relating to methods of treating the waste liquors obtained in the decomposition of lignified cellulose-containing materials |
| US2906659A (en) * | 1953-07-13 | 1959-09-29 | Abitibi Power & Paper Co | High yields bisulphite pulping process |
| FR1173329A (en) * | 1957-03-25 | 1959-02-24 | Crown Zellerbach Corp | Manufacture of dimethyl sulfide from pulp mill waste liquors |
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