CN115874479B - Alkaline acid pulping process and engineering for recycling raw materials - Google Patents
Alkaline acid pulping process and engineering for recycling raw materials Download PDFInfo
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- CN115874479B CN115874479B CN202111155597.3A CN202111155597A CN115874479B CN 115874479 B CN115874479 B CN 115874479B CN 202111155597 A CN202111155597 A CN 202111155597A CN 115874479 B CN115874479 B CN 115874479B
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- pulping
- calcium
- solution
- acid
- pulp
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- 238000000034 method Methods 0.000 title claims abstract description 221
- 238000004537 pulping Methods 0.000 title claims abstract description 176
- 230000008569 process Effects 0.000 title claims abstract description 103
- 239000002994 raw material Substances 0.000 title claims abstract description 64
- 239000002253 acid Substances 0.000 title claims abstract description 61
- 238000004064 recycling Methods 0.000 title abstract description 12
- 239000003337 fertilizer Substances 0.000 claims abstract description 83
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims abstract description 80
- YAECNLICDQSIKA-UHFFFAOYSA-L calcium;sulfanide Chemical compound [SH-].[SH-].[Ca+2] YAECNLICDQSIKA-UHFFFAOYSA-L 0.000 claims abstract description 36
- 239000000463 material Substances 0.000 claims abstract description 26
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims abstract description 24
- 235000011941 Tilia x europaea Nutrition 0.000 claims abstract description 24
- 239000004571 lime Substances 0.000 claims abstract description 24
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 127
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 54
- 239000000243 solution Substances 0.000 claims description 54
- 239000003513 alkali Substances 0.000 claims description 51
- 241000196324 Embryophyta Species 0.000 claims description 45
- 239000007788 liquid Substances 0.000 claims description 41
- 229920005610 lignin Polymers 0.000 claims description 40
- GBAOBIBJACZTNA-UHFFFAOYSA-L calcium sulfite Chemical compound [Ca+2].[O-]S([O-])=O GBAOBIBJACZTNA-UHFFFAOYSA-L 0.000 claims description 39
- 235000010261 calcium sulphite Nutrition 0.000 claims description 39
- 235000010269 sulphur dioxide Nutrition 0.000 claims description 39
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 35
- 239000011591 potassium Substances 0.000 claims description 35
- 229910052700 potassium Inorganic materials 0.000 claims description 35
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 33
- 241001330002 Bambuseae Species 0.000 claims description 31
- 239000003795 chemical substances by application Substances 0.000 claims description 31
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 30
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 30
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 30
- 239000011425 bamboo Substances 0.000 claims description 30
- 239000000047 product Substances 0.000 claims description 27
- 238000009835 boiling Methods 0.000 claims description 23
- 238000010168 coupling process Methods 0.000 claims description 22
- 230000008878 coupling Effects 0.000 claims description 20
- 238000005859 coupling reaction Methods 0.000 claims description 20
- 238000001914 filtration Methods 0.000 claims description 20
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 18
- 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 18
- 238000002791 soaking Methods 0.000 claims description 18
- 239000010902 straw Substances 0.000 claims description 17
- 239000000706 filtrate Substances 0.000 claims description 16
- 239000010440 gypsum Substances 0.000 claims description 16
- 229910052602 gypsum Inorganic materials 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 13
- 238000004898 kneading Methods 0.000 claims description 13
- 229920001732 Lignosulfonate Polymers 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 241000233866 Fungi Species 0.000 claims description 10
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 10
- 239000000920 calcium hydroxide Substances 0.000 claims description 10
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 10
- 235000011116 calcium hydroxide Nutrition 0.000 claims description 9
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical group [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 claims description 9
- 235000019252 potassium sulphite Nutrition 0.000 claims description 9
- 229920005551 calcium lignosulfonate Polymers 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000000354 decomposition reaction Methods 0.000 claims description 8
- 230000020477 pH reduction Effects 0.000 claims description 8
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 241001494508 Arundo donax Species 0.000 claims description 7
- 244000025254 Cannabis sativa Species 0.000 claims description 7
- 235000014676 Phragmites communis Nutrition 0.000 claims description 7
- 238000006386 neutralization reaction Methods 0.000 claims description 7
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 7
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 7
- 235000011151 potassium sulphates Nutrition 0.000 claims description 7
- 230000001502 supplementing effect Effects 0.000 claims description 7
- 229920000742 Cotton Polymers 0.000 claims description 6
- 238000012545 processing Methods 0.000 claims description 6
- 230000009467 reduction Effects 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 claims description 5
- 238000004090 dissolution Methods 0.000 claims description 5
- 240000007594 Oryza sativa Species 0.000 claims description 4
- 235000007164 Oryza sativa Nutrition 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 235000009566 rice Nutrition 0.000 claims description 4
- 235000010265 sodium sulphite Nutrition 0.000 claims description 4
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 3
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 3
- 230000003472 neutralizing effect Effects 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 241000609240 Ambelania acida Species 0.000 claims description 2
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 2
- 244000060011 Cocos nucifera Species 0.000 claims description 2
- 244000068988 Glycine max Species 0.000 claims description 2
- 235000010469 Glycine max Nutrition 0.000 claims description 2
- 241000219146 Gossypium Species 0.000 claims description 2
- 240000006394 Sorghum bicolor Species 0.000 claims description 2
- 235000011684 Sorghum saccharatum Nutrition 0.000 claims description 2
- 235000021307 Triticum Nutrition 0.000 claims description 2
- 244000098338 Triticum aestivum Species 0.000 claims description 2
- 240000008042 Zea mays Species 0.000 claims description 2
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims description 2
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 2
- 239000010905 bagasse Substances 0.000 claims description 2
- 235000005822 corn Nutrition 0.000 claims description 2
- 239000012047 saturated solution Substances 0.000 claims description 2
- 239000006228 supernatant Substances 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 239000004295 calcium sulphite Substances 0.000 claims 3
- 239000004291 sulphur dioxide Substances 0.000 claims 3
- 239000005864 Sulphur Substances 0.000 claims 1
- 229920005550 ammonium lignosulfonate Polymers 0.000 claims 1
- 238000010790 dilution Methods 0.000 claims 1
- 239000012895 dilution Substances 0.000 claims 1
- 238000010979 pH adjustment Methods 0.000 claims 1
- 238000009738 saturating Methods 0.000 claims 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 18
- 239000011593 sulfur Substances 0.000 abstract description 5
- 229910052717 sulfur Inorganic materials 0.000 abstract description 5
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 abstract 1
- 125000004122 cyclic group Chemical group 0.000 abstract 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 36
- JXRVKYBCWUJJBP-UHFFFAOYSA-L calcium;hydrogen sulfate Chemical compound [Ca+2].OS([O-])(=O)=O.OS([O-])(=O)=O JXRVKYBCWUJJBP-UHFFFAOYSA-L 0.000 description 17
- 239000000835 fiber Substances 0.000 description 15
- 238000012360 testing method Methods 0.000 description 15
- 235000011121 sodium hydroxide Nutrition 0.000 description 14
- 239000006227 byproduct Substances 0.000 description 13
- 238000010025 steaming Methods 0.000 description 13
- 239000002002 slurry Substances 0.000 description 12
- 239000002689 soil Substances 0.000 description 11
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- 244000302661 Phyllostachys pubescens Species 0.000 description 10
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- 238000010411 cooking Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 235000015097 nutrients Nutrition 0.000 description 10
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 9
- 229910052791 calcium Inorganic materials 0.000 description 9
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 9
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- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- 230000008901 benefit Effects 0.000 description 6
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 4
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- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
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- 239000002244 precipitate Substances 0.000 description 3
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- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 3
- 239000002023 wood Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
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- 239000007832 Na2SO4 Substances 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
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- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 2
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Abstract
The invention relates to an alkaline pulping process and an acid pulping process and engineering for recycling raw materials, in particular to a production system and a related process for preparing unbleached pulp by using acid low-concentration calcium bisulfide and sulfur dioxide and lime in the alkaline pulping process. The full cyclic application of the materials containing the calcium element and the sulfur element in the two processes is realized, and the bio-based water-soluble fertilizer can be co-produced.
Description
Technical Field
The technology belongs to the field of deep processing and application of biomass, and relates to an alkaline acid pulping process and engineering for recycling raw materials.
Background
Biomass scale and low cost processing and full price utilization are fundamental directions of human society development, and pulping and papermaking and bio-based materials are national economy basic industries which meet the requirements of sustainable development strategy and have great development potential.
The annual pulp consumption of Chinese paper exceeds 1 hundred million tons, and the production of pulping raw materials is limited due to the forbidden forest and ecological environment protection, so that the current primary pulp yield is less than 2000 ten thousand tons/year. Waste paper regeneration is a main way of papermaking raw materials, but has the problems of only about 70% of pulp recovery rate, poor quality and safety of recovered pulp, serious secondary pollution in the recovery processing process and products, and the like. Waste paper import is completely prohibited in 2021 in China for 1 month and 1 day, huge gaps appear in pulp raw material supply in the papermaking industry due to the completely tightened waste limit, the pulping and papermaking industry faces multiple challenges, and many pulping and papermaking factories are forced to be closed in a large amount due to the fact that raw materials cannot be guaranteed, cannot reach standards, and the problems of high energy consumption, high cost and the like. Obviously, the clean pulping and biomass full-value utilization technology of non-wood raw materials can be greatly developed according to local conditions, the autonomous and controllable industry chain and the country vibration strategy can be better implemented, and the trillion-level green pulping and papermaking with the reputation of white metallurgy and the rapid development of new material industry can be strongly promoted. Obviously, the rich or dominant biomass raw materials such as straw, processing residues, bamboo, arundo donax, reed and the like are developed and fully utilized, and the novel clean pulping production process has great significance in realizing 'wood substitution' and ecological development.
Bamboo is one of the fastest growing plants, especially the dry basis yield of artificially cultivated super bamboo and dominant pasture can reach more than 5 tons/mu, the bamboo pulp is a dominant resource type plant with ecological restoration and 'carbon neutralization' of great value, alkali recovery is difficult due to concentration scaling, the main bamboo species common in all places, namely the bamboo is thick and dense to pulp, obviously, the development can break the difficult problem, the technical bottleneck of pulping and papermaking industry is overcome, the bamboo pulp can be widely applied to the full-cost and low-cost utilization of various plant raw materials (including the raw materials of the bamboo which is difficult to pulp, the most ecological restoration value and growth advantage and can mechanically harvest, namely the bamboo and 'oasis first-class' pasture and straw) and the like, and the clean pulping process for producing high-quality products with high yield is a biomass splitting and depolymerizing technology with 'subversion' which can solve the pain points of industry and is the important points, bright points and fulcraps of developing biology-based industry chains.
Pulping is a production process that separates plant materials into pulp by chemical, mechanical, biological or a combination of the above methods. Depending on the digestion and refining process, chemical, semi-chemical, chemimechanical, mechanical and biological pulps may be produced with varying yields, properties and qualities.
The chemical pulping methods commonly adopted in the paper industry at present mainly comprise alkaline pulping, sulfite pulping and solvent pulping. The alkaline pulping method comprises caustic soda process, sulfate process, sodium polysulfide process, prehydrolysis sulfate process, oxygen alkaline process, lime process, soda process, etc. The most common are the sulfate and caustic soda processes. The sulfite pulping mainly comprises an acidic bisulfite method, a subacidic bisulfite method, a neutral salt sulfate method and an alkaline sulfite method.
The traditional sulfate alkaline process has the advantages of wide application range of raw materials, high delignification rate, short cooking time, high pulp strength and perfect cooking waste liquid recovery technology and equipment. However, the three wastes are serious, and the problems of high post-treatment difficulty, high investment, high cost, high energy consumption and the like exist, and 2 to 3 tons of absolute dry plant raw materials and 0.67 to 0.9 ton of sodium hydroxide are needed to obtain 1 ton of fiber slurry. The large amount of alkali is used to damage fiber and lignin, thus causing high raw material consumption and pulping cost, waste of resources and difficult recycling of a large amount of papermaking black liquor. At present, incineration is considered as a feasible method for solving the pollution of papermaking black liquor, the pollution problem of pulping black liquor is partially solved by concentrating, incinerating and causticizing the pulping black liquor, but secondary pollution exists, a large amount of lignin and hemicellulose dissolved in the pulping black liquor only uses the energy of the pulping black liquor, the pulping black liquor is not used as a resource with more added value, equipment investment is large, cost is high, energy consumption is large, the investment of the whole black liquor concentrating and incinerating system is large (more than half of the total investment), and a large amount of carbon dioxide, nitrogen oxides, sulfur dioxide, dioxin waste gas, white mud waste residues with residual alkali, sodium sulfide, aluminosilicate and the like and mainly containing calcium carbonate are discharged, and secondary pollution exists. Black liquor containing very high silicate, such as straw, is easy to concentrate and scale, and the operation effect is not ideal.
The alkaline or neutral sodium sulfite solution is heated to be steamed and pulped under hot belt pressure, or sodium bisulphite is steamed and pulped in an acidic solution, and the pulping process can be carried out smoothly under the process condition of long-time steaming and boiling for about 3 hours at the high temperature of about 170 ℃, the obtained pulp has low strength, the byproduct of the pulping liquid which takes sodium lignin sulfonate as the main component and has better water solubility but complex components is seriously degraded in lignin and hemicellulose, the high molecular performance is lost, and the pulping liquid is used as a concrete water reducing agent or emulsifying agent such as petroleum, asphalt, pesticide and the like with low purity requirement. Because of poor service performance and instability caused by the interference of salt and small molecules, the lignin sulfonic acid is usually recovered by adopting acidification precipitation, water-soluble salts and small molecules are removed, and the water-soluble lignin calcium can be produced by using a method of lime neutralization, so that the product performance is improved, but the problems of low yield, high-concentration salt-containing mother liquor wastewater needing biochemical treatment and discharge, high production cost, small product market and the like still exist; because the bisulphite method has the problems of degradation, poor slurry quality, high equipment cost, serious corrosion and environmental pollution and the like under the condition of long-time high temperature, enterprises adopting the pulping process of the acid method are basically not adopted.
In general, on one hand, chemical pulping such as alkaline pulping, acid pulping, sulfate pulping and the like, including mechanical pulping, semi-mechanical pulping and microbial pulping, are limited by a plurality of factors such as raw materials, investment, technology, cost, quality, efficiency, environmental protection and the like to face development bottlenecks, and especially pulping black liquor cannot expand effective use, and the current alkali recovery or lignin sulfonate recovery has high cost, secondary pollution and needs to be subjected to 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. The pulping principle of the process is mainly based on that phenolic hydroxyl groups of lignin can form phenolic oxygen anions with alkali to form salt, the strong like-charge repulsion effect among the phenolic oxygen anions can promote the lignin to be disassembled and peeled from plant tissues, the soft dissociation process can be promoted by stewing, the softened raw materials are most thinned and ground into pulp, the energy consumption is low, the fiber breakage is effectively avoided, and the strength of the pulp is well maintained. Under the optimized alkali amount, soaking time, concentration and temperature conditions, the high-quality unbleached pulp can be obtained with high yield, and the potassium lignin dissolved in the night can be directly used as a liquid fertilizer or an acid soil conditioner or a nutrient matrix component. However, the production process of co-producing the potassium-rich organic fertilizer by a potassium method (a pulping method using potassium hydroxide as a resolving agent in alkaline pulping) 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.
Based on the prior development foundation, in order to overcome the problems, the subject group carries out continuous and deep technological innovation research, and a new breakthrough is made in the aspect of key node technology of biomass splitting, depolymerizing, cleaning and pulping and better application of pulping, so that biomass is utilized in a large scale, low cost, high efficiency, cleaning and full price, and an ecological industry group is possibly innovated.
Disclosure of Invention
In order to solve the problems, the invention provides a method for recycling part of raw materials and by-producing high-value fertilizer in acid pulping, and also provides a method for using sulfur-containing raw materials and calcium-containing raw materials in pulping by combining an acid method and an alkali method, so that the pulping cost is obviously reduced, the emission of waste in pulping is reduced, and meanwhile, the quality of the by-product fertilizer can be obviously improved.
The invention provides a novel process for co-producing bio-based water-soluble fertilizer by acid method and coupling pulping of acid method and alkali method, wherein the alkali method process is a process of co-producing water-soluble lignin potash fertilizer by potassium hydroxide or sodium hydroxide or adopting sodium hydroxide or potassium hydroxide without black liquor pulping as a resolving agent, the novel process of acid method adopts low-dosage calcium bisulfide catalyzed by strong acid as the resolving agent, has the capability of obviously improving and softening various plant raw materials, particularly difficult-to-pulp raw materials such as moso bamboo and the like, can greatly improve the pulp yield and whiteness, and simultaneously co-produces lignin calcium sulfonate water-soluble fertilizer. The specific technical scheme is as follows: preferably, the potassium salt black liquor obtained by pulping the mixed raw materials of potassium hydroxide or potassium sulfate, potassium sulfite, plant ash and other potassium salt and lime combined double decomposition capable of generating potassium hydroxide are taken as a resolving agent, and can be used as a water-soluble fertilizer or an acid soil conditioner, and sulfur dioxide or sulfurous acid can be used for acidizing and recycling lignin or producing modified natural-color fiber pulp. The separated sulfite-containing filtrate is regenerated by slaked lime to obtain a potassium hydroxide-containing resolving agent solution, the potassium hydroxide-containing resolving agent solution complements the lost alkali, the solution is recycled to be used in an alkali pulping process, the separated calcium sulfite precipitate is continuously introduced with sulfur dioxide to be converted into water-soluble calcium bisulfide, the water-soluble calcium bisulfide is acidified by sulfuric acid to be used as an acid-based pulping and acid-base resolving agent raw material for co-production of water-soluble bio-based calcium sulfonate, the novel acid-base coupling novel process can realize remarkable energy conservation, consumption reduction and high-yield pulping, the multifunctional bio-based water-soluble fertilizer can be co-produced according to the requirement, the problem that raw materials such as moso bamboo and the like are difficult to pulp is broken, the pulping raw material range is widened, the full-value high-value utilization of plant raw materials is realized, and the production cost of unbleached pulp and the water-soluble fertilizer can be greatly reduced.
Specifically, the invention provides a novel process for producing a substance-based water-soluble fertilizer by coupling pulping through an acid method and pulping through an alkali method, which is characterized in that the pulping through the alkali method is to use a solution containing potassium hydroxide or sodium hydroxide as a resolving agent for pulping, the pulping through the acid method is to use a solution containing sulfuric acid and calcium bisulfide as the resolving agent for pulping, the pulping through the alkali method is to obtain black liquor, unbleached pulp or a mixture of the black liquor and unbleached pulp, a product containing biological-based sulfonate is obtained through sulfonation of sulfur dioxide or a sulfurous acid solution, the product is filtered to obtain a filtrate, the filtrate is subjected to causticization and conversion by slaked lime to obtain calcium sulfite, the regenerated potassium hydroxide or sodium hydroxide filtrate is recycled for pulping through the alkali method under the condition of supplementing the lost alkali amount, and the filtered or simply separated calcium sulfite-enriched filter residues are added into an aqueous solution for being used, and the sulfuric dioxide or the sulfuric acid solution is added for acidification and dissolution into the aqueous solution of calcium bisulfide for pulping through the acid method.
Preferably, in the novel technology for producing the bio-based water-soluble fertilizer by coupling pulping by an acid method and pulping by an alkali method in parallel, the technology for pulping by the acid method comprises the following steps: soaking and steaming plant raw materials in a solution containing sulfuric acid and calcium bisulfide, and then kneading, pulping and filtering to obtain unbleached pulp and red liquor, wherein the solid-liquid ratio of the plant raw materials to the calcium bisulfide solution is 1: 3-10, wherein the dosage of the calcium bisulfide in the calcium bisulfide solution is 5-15% of the absolute dry plant mass, the pH value of the calcium bisulfide solution is 1-5, the soaking and steaming temperature is 80-130 ℃, and the steaming time is 2-6h.
Preferably, in the novel process for producing the substance-based water-soluble fertilizer by coupling pulping by an acid method and pulping by an alkali method, pulping red liquid filtered in the pulping by the acid method is supplemented with calcium sulfite and is introduced with sulfur dioxide or added with a sulfurous acid solution for acidification and can be recycled, after nearly saturated recycling, the substance-based water-soluble fertilizer raw material or fertilizer product mainly comprising calcium lignosulfonate can be neutralized and co-produced, or the partially extracted red liquid can be neutralized and diluted to be directly used as a liquid fertilizer, or the precipitated calcium sulfate is separated after adding potassium sulfate or ammonium sulfate into the red liquid to obtain a solution containing potassium lignosulfonate or ammonium sulfate, and the solution can be directly used as a fertilizer or concentrated to be a liquid fertilizer or a powder water-soluble fertilizer product after pH value of the solution neutralization is adjusted to 6-8.
The novel process for producing the bio-based water-soluble fertilizer by coupling pulping by the acid method and the alkaline method can obviously save energy, reduce consumption, reduce production cost and environmental pollution, recycle calcium-containing and sulfur-containing materials, and produce a green product with high added value.
Preferably, in the novel process for producing the substance-based water-soluble fertilizer by coupling pulping by an acid method and pulping by an alkali method in parallel, the amount of calcium bisulfide finally supplemented by pulping red liquid is 5-15% of the mass of absolute dry plants.
Preferably, in the novel process for producing the bio-based water-soluble fertilizer by coupling pulping by an acid method and pulping by an alkali method in parallel, the pH value of the solution containing sulfuric acid and calcium bisulfide is 1-2, the cooking time is 2-3 hours, and the cooking pressure is normal pressure or less than 2 times of atmospheric pressure.
Preferably, in the novel process for producing the bio-based water-soluble fertilizer by coupling pulping by an acid method and pulping by an alkali method in parallel, the process for pulping by the alkali method comprises the following steps: soaking and boiling plant materials in a solution containing potassium hydroxide or sodium hydroxide, kneading and pulping to obtain a mixture of unbleached pulp and black liquor, introducing sulfur dioxide or adding an aqueous solution of sulfurous acid to acidify to pH 1-5, filtering, separating and washing to obtain unbleached pulp and filtrate which are rich in lignin, wherein the main component of the filtrate is potassium sulfite or sodium sulfite, adding lime or slaked lime pulp into the filtrate to stir and mix, precipitating, applying supernatant containing potassium hydroxide or sodium hydroxide or filtrate serving as a resolving agent of an alkaline pulping process to the next alkaline pulping process, circularly applying a near-saturated solution, adjusting the pH to produce a water-soluble lignin potassium fertilizer or a liquid fertilizer product, mixing precipitated and separated calcium sulfite solid with red liquor of the acid pulping, introducing sulfur dioxide or adding the aqueous solution of sulfurous acid to acidify to pH 1-5, dissolving and converting calcium sulfite into a water-soluble strong calcium sulfite solution, and applying the calcium sulfite as a resolving agent to the acid pulping process, and obtaining a water-soluble raw material or liquid fertilizer product which is rich in lignin calcium sulfonate after the circulating saturation.
Preferably, in the novel process for producing the bio-based water-soluble fertilizer by coupling pulping by an acid method and pulping by an alkali method in parallel, sulfur dioxide is introduced or a sulfurous acid aqueous solution is added for acidification until the pH is 3-5.
Preferably, in the novel process for producing the bio-based water-soluble fertilizer by coupling pulping by an acid method and pulping by an alkali method in parallel, the method is characterized in that sulfur dioxide is sulfur dioxide obtained by decomposing calcium sulfite, or sulfur dioxide is obtained by reducing desulfurization gypsum, phosphogypsum or fluorgypsum or natural gypsum at a high temperature in a kiln, or sulfur dioxide is obtained by burning sulfur, and lime is lime obtained by decomposing the calcium sulfite, or lime obtained by reducing desulfurization gypsum, phosphogypsum or fluorgypsum or natural gypsum at a high temperature in the kiln.
Preferably, in the novel process for producing the bio-based water-soluble fertilizer by coupling pulping by an acid method and pulping by an alkali method in parallel, the novel process uses plant raw materials and lime, plant ash and sulfur dioxide as raw materials, and uses 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 uses the acid resolving agent to independently prepare two kinds of pulp and co-produce the two bio-based water-soluble fertilizers by coupling the acid method and the alkali method.
Preferably, in the novel process for producing the substance-based water-soluble fertilizer by coupling pulping by an acid method and pulping by an alkali method, the performance of the natural color pulp produced by the acid method, the alkali method and the coupling process thereof in equal proportion can be close to that of the alkali method process with better performance, and the performance of the mixed paper of different raw materials can be enhanced or maintained, so that the mixed pulp produced by different processes has more cost performance advantages by using different raw materials, and the acid method pulp produced by the acid method and the natural color pulp obtained by the alkali method can be mixed according to the strength requirements of paper products or other fiber photos.
The invention also provides a method for synthesizing the high-yield unbleached pulp and the fertilizer rich in potassium lignin, calcium lignosulfonate and/or potassium lignosulfonate, which comprises the following steps:
Soaking and steaming plant raw materials in a solution containing sulfuric acid and calcium bisulfide, and then kneading, pulping and filtering to obtain unbleached pulp and red liquor, wherein the solid-liquid ratio of the plant raw materials to the calcium bisulfide solution is 1: 3-10, wherein the dosage of the calcium bisulfide in the calcium bisulfide solution is 5-15% of the absolute dry plant mass, the pH value of the calcium bisulfide solution is regulated to 1-5 by sulfuric acid, the soaking and steaming temperature is 80-130 ℃, and the steaming time is 2-6h;
Soaking and boiling plant materials in alkaline potassium hydroxide solution, kneading, pulping, filtering to obtain unbleached pulp and black liquor,
Mixing the red liquor and the black liquor, neutralizing, and filtering to separate out fertilizer raw materials or fertilizer products containing calcium sulfite and rich in potassium lignin, potassium lignin sulfonate and calcium lignin sulfonate.
Preferably, in the above method, the plant material is one or more of bamboo, fungus grass, arundo donax, reed, crop straw, bagasse, coconut shell, cotton stalk, bamboo wood processing residues, the crop straw is wheat, rice, corn, soybean, sorghum, cotton straw, preferably, the plant material is bamboo, particularly preferably, the bamboo is crushed bamboo, particularly preferably, the plant material is bamboo, fungus grass, arundo donax, crop straw, reed, cotton stalk.
Preferably, in the above method, the fertilizer raw material is concentrated to more than 50% of concentrated liquid product or spray-dried into powder product as fertilizer.
Preferably, in the above method, the main component of the black liquor in the alkaline pulping method is potassium lignin, and the main component of the red liquor in the acid pulping method is calcium lignin sulfonate.
Preferably, in the above alkaline pulping method, the lime or quicklime is added in an amount not less than the sulfite reaction amount.
Based on the analysis and the breakthrough results of the acid pulping process, lignin is recovered by replacing sulfuric acid or lignin salt solution in the sulfuric acid aluminate alkaline process and the non-night process with sulfur dioxide to improve the pulp yield, and the method that calcium sulfite with two orders of magnitude smaller than the solubility product of calcium sulfate and completely and most produce potassium hydroxide can be added into filtrate to solve the problems of incomplete double decomposition and conversion, slow conversion, serious lime entrainment and the like of the potassium sulfate and the slaked lime process, so that the potassium hydroxide can be regenerated more thoroughly and recycled. The method for adding the precipitated and separated calcium sulfite into the circulating liquid and then introducing sulfur dioxide to dissolve and convert the calcium sulfite into the acid pulping resolving agent of the calcium bisulfate realizes the reutilization of calcium resources and the ingenious coupling of the acid process and the alkali process. Compared with the existing potassium sulfite, sodium sulfite or ammonium sulfite which needs about 160 ℃ of reaction temperature, longer reaction time and larger dosage of the splitting agent under acidic, neutral or alkaline conditions, the method has the advantages of more cost performance and mild production conditions.
In the pulping method, the byproduct pulping liquid 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 protein-rich straw is the raw material capable of being recycled in a large amount. The application evaluation results show that the biological-based sulfonate taking the potassium lignin, the calcium lignin sulfonate and the straw as raw materials can be independently and mutually combined or compounded with nitrogen, phosphorus and potassium fertilizers to form a series of products with various functions of fertilizer conservation, water conservation, fertilizer supply, water absorption, comprehensive balance nutrition supply, sand fixation, skinning, alkali inhibition by binding salt, complexation dissolution assistance, ecological restoration and the like, and can be used as a series of biological nutrition sources such as deserts, saline-alkali lands, fields, facility agriculture, gardens, acid-alkali soil conditioning, nutrition matrixes, edible fungus culture mediums and the like, and can be called as artificial mannose, and the potassium lignin, the potassium lignin sulfonate, the calcium lignin sulfonate or the calcium lignin sulfonate which are prepared and combined in pulping are the core functional components.
The invention not only can make up the defects of the prior pulping process, but also can reduce the degradation and damage of plant macromolecules, improve the quality of the pulp, ensure the stability and the solubility of water-soluble macromolecules in a large pH value range, and can play a role of complexation and dissolution assistance.
The invention initiates a new acid method, a new alkali method and a new method for pulping by coupling raw materials of the acid method and the alkali method and co-producing water-soluble fertilizer. The novel process for independent pulping by taking plants, lime and sulfur dioxide as raw materials, taking potassium hydroxide or regenerated potassium hydroxide solution as an alkaline resolving agent and calcium bisulfide as an active component and an acid resolving agent and respectively pulping and coproducing the bio-based water-soluble fertilizer by coupling an acid process and an alkali process is developed: 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, and then carrying out double decomposition reaction on potassium sulfite and slaked lime in the neutralized filtrate to regenerate potassium hydroxide aqueous solution for recycling. 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 and skillfully couple 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.
In conclusion, the research and development team creates novel processes of an acid method and an alkali method and novel processes of co-production of high-yield and high-quality unbleached pulp and co-production of bio-based water-soluble fertilizer by coupling the acid method and the alkali method, and the novel processes are significant 'subversion' technical 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.
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.
The potassium-method slurry or the calcium sulfite-method slurry can be reused for many times until the solution is saturated after the resolving agent and the washing water are supplemented, and the most part of the solution can be reused and the less part of the concentrated solution can be extracted, so that the energy saving and the consumption reduction can be realized to the greatest extent, and the cost can be reduced.
The alkaline black liquor taking the potassium lignin extracted by the pulping method as a main component or the acid red liquor taking the calcium lignin sulfonate as a main component can be directly diluted or acidified according to the use requirement, or the black liquor and the red liquor are compounded for use according to local conditions, and the black liquor and the red liquor can be concentrated, spray-dried liquid fertilizer or water-soluble solid products and can be compounded with pulp, biomass, organic fertilizer and chemical fertilizer singly or jointly to form paper film fertilizer, nutrient substrate, edible fungus culture medium, sustained and controlled release fertilizer, water-soluble fertilizer, biological organic fertilizer and 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 biggest point of the invention is to utilize the characteristics that the solubility of calcium sulfite is two orders of magnitude lower than that of calcium sulfate and the solubility of calcium bisulfate is much higher than that of calcium sulfate, realize to replace expensive KOH or NaOH with the combination of cheap lime and sulfur dioxide, and invent a novel coupled pulping process, and initiate a novel process of pulping with high yield under the mild condition of calcium bisulfate and co-producing water-soluble lignin sulfonate biological base fertilizer and soil conditioner. The pulping cost of the invention is only about one third of the cost of the existing alkaline method and alkaline recovery process (the comprehensive cost of the natural-color air-dried pulp withholding the value of a byproduct is about 1000 yuan/ton), and the invention can clean and produce high-quality natural-color pulp by using various industrial and agricultural three-waste raw materials, and simultaneously coproduce the water-soluble fertilizer with good use effect and wide application range. The new process has mild condition, high utilization rate of raw materials, good protection of the biological macromolecular structure of the raw materials and products, small equipment investment and small corrosion. The invention can use circulating feed liquid with lower concentration (about 2.5%) of calcium bisulfate and potassium hydroxide (about 3.5%), respectively and independently pulp or pulp and mix pulp for papermaking in a coupling way at a lower soaking and steaming temperature (80-130 ℃) and a shorter time (1-3 hours), and coproduce water-soluble fertilizers and soil conditioners such as calcium lignosulfonate or produced 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, avoiding secondary pollution, producing high-quality unbleached pulp and water-soluble biological base fertilizers and soil conditioners with excellent coproduction performance in high efficiency, simple and convenient land and large scale, and being widely used for the ecological restoration of deserts, saline-alkali lands and other deserts, the soil conditioning of fields and greenhouses, the high-standard farmland construction and the yield and quality improvement of crops.
The black liquor and the red liquor can be concentrated, spray-dried liquid fertilizer or water-soluble solid product, and can be singly or jointly compounded with slurry, biomass, organic fertilizer, chemical fertilizer, calcium salt, aluminum salt, medium and trace nutrient elements, phosphate, sulfate, silicate and the like to form paper film fertilizer, nutrient matrix, edible fungus culture medium, sustained and controlled release fertilizer, water-soluble fertilizer, biological organic fertilizer and foliar fertilizer for use, thereby further providing and balancing full nutrition, improving water-retention and water-saving efficiency, and preventing dissolution, water retention and fertilizer-retention effects of nutrient components.
The invention solves the problems of high production cost, secondary pollution, difficult recycling of a large amount of pulping liquid and the like of the pulping process in China, can promote the effective utilization of raw materials such as moso bamboo, straw, industrial byproduct gypsum and the like, builds ecological restoration and ecological industry groups, breaks biomass into split, depolymerizes and grades for utilization, and creates a bio-based industry chain, thereby opening up a new way.
In the alkaline pulping method or the acid pulping method, aluminum sulfate is added in the processes of steaming, spraying, kneading, pulp extruding and/or pulping to uniformly flocculate and sediment and adsorb macromolecules such as lignin dissolved in water on fibers, so that the yield and the performance of the unbleached pulp are effectively improved, and the addition amount of the aluminum sulfate can be 0.5 to 30 percent of the weight of the fibers.
The alkaline pulping or calcium bisulfate pulping can be reused for many times after the resolving agent and the washing water are supplemented, until the solution is saturated, most of the alkaline pulping or calcium bisulfate pulping can be reused to produce a small part of concentrated solution, so that the energy saving and consumption reduction can be realized to the greatest extent, and the production cost can be reduced.
The mild pulping conditions ensure that the biological macromolecular structures such as lignin and the like are well protected, and the pulping liquid is rich in water-soluble nutrient components such as lignin and biological nutrient elements such as calcium, potassium, nitrogen, phosphorus and the like, can be used as biological nutrient sources and biological energy sources, and can be used as main functional components of water-soluble fertilizers, paper-based mulch fertilizers, biological matrixes, edible fungus culture mediums, foliar and root fertilizers and soil conditioners.
Drawings
FIG. 1 is a process route diagram of acid-process alkaline-process coupled pulping and water-soluble fertilizer co-production;
FIG. 2 is a graph showing appearance and color comparison of each processed boiled bamboo strip;
FIG. 3 shows a paper product produced from moso bamboo pulp prepared by a potassium hydroxide method;
FIG. 4 acid paper under acid-base coupling process;
FIG. 5 is an infrared spectrum of alkali lignin potassium;
FIG. 6 shows a nuclear magnetic resonance spectrum of potassium lignin by an alkali method.
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: air-dried pulp yield of pulping of different splitting agents and plant materials according to a sectional process
100G of bamboo chips are treated in a sectional manner by using different splitting agents: soaking at 60deg.C for 12 hr, steaming at 125deg.C for 2.5 hr, cooling, taking out bamboo chips, kneading, pulping, sieving, fiber dissociating, filtering, oven drying, and calculating pulp yield. The beating degree is controlled to be 40 DEG SR, the paper ration is 80g/m 2, and the strength is measured by papermaking. The yields of air dried pulp prepared under various process conditions and having a moisture content of about 10% are shown in the following table.
Table 1 air dried pulp yield of pulp prepared by alkaline process with different resolving agents and process
| Numbering device | Resolving agent | Dosage of resolving agent | Process conditions | Yield of air-dried pulp |
| 1-1 | NaOH and Na 2 S | 20g | 100G of folded bamboo; solid-to-liquid ratio 1:4.2 | 59.5％ |
| 1-2 | NaOH | 10g | 100G of folded bamboo; solid-to-liquid ratio 1:4.2 | 70.5％ |
| 1-3 | KOH | 10g | 100G of folded bamboo; solid-to-liquid ratio 1:4.2 | 71.0％ |
| 1-4 | Ca(OH)2/Na2SO4 | 8g | 100G of folded bamboo; solid-to-liquid ratio 1:10 | 75.1％ |
The air-dried pulp in table 1 was subjected to papermaking, and the properties of the paper patterns are shown in table 2.
Table 2 results of comparative analysis of papermaking properties of sodium and potassium processes
The experimental results show that: the paper sample made of the unbleached pulp prepared under the condition of pressure cooking has the best performance of Na method and K method, the strength performance of the pulp sample is similar, when the beating degree is about 45 DEG SR, the folding endurance is 10-110 times, the tearing index is 10.0-13.0 mN.m 2/g, the tensile index is 43.0-50.0 N.m/g, the bursting index is 2.8-4.20 kPa.m 2/g, the individual performance of the K method pulp is slightly better than that of the Na method pulp, the damage effect of the raw material KOH on lignin and fiber is stronger than that of NaOH, so that the prepared pulp is softer than that of NaOH, and the individual index is higher than that of the Na method pulp in physical property; the pulping yield of the Ca (OH) 2/Na2SO4 composite alkali by the black liquor-free calcium method is higher, but the problems of lower pulp strength and difficult gypsum separation exist.
Example 2: evaluation of concentrating effect of calcium bisulfate method slurry sleeve
Test one: adding 200g of phyllostachys praecox chips into a digester, adding 1000ml of calcium bisulfate splitting agent aqueous solution, wherein the dosage of the calcium bisulfate is 20g, adding 4g of concentrated sulfuric acid to adjust the pH to about 1.5, cooking in the temperature range of 120-130 ℃ for 2.5-3 h, taking out softened materials for kneading after cooling after cooking, pulping, screening pulp, dissociating fibers, filtering and drying, and calculating the pulp yield. The beating degree is controlled to be 40 DEG SR, the paper ration is 80g/m 2, the paper is made, and the mechanical property is tested.
And (2) testing II: adding 200g of folded moso bamboo chips into a digester, continuously supplementing required amount of calcium sulfite into the red liquid after separating the pulp, introducing sulfur dioxide to pH of 5, adding concentrated sulfuric acid to adjust pH to 1.5, cooking in a temperature range of 120-130 ℃ for 2.5-3 h, taking out softened materials for kneading, pulping, screening pulp, dissociating, filtering and drying fibers, and evaluating pulping effect. The red liquid component is analyzed, so that calcium sulfite can be supplemented and sulfur dioxide is introduced to prepare calcium bisulfate for continuous application.
Table 3 test results of red liquid properties obtained by recycling pulping liquor prepared by calcium bisulfide method
Table 4 shows the performance test results of the natural color slurry prepared by circularly applying the calcium bisulfate method to the slurry
The test shows that: continuous application of the calcium sulfite prepared by supplementing the calcium sulfite to prepare the calcium bisulfate is feasible by analyzing the red liquid component, the solid content of the red liquid is improved along with the increase of the application times, the whiteness and the quality of the pulp are improved along with the increase of the application times, and the presence of the byproduct calcium lignosulfonate is proved to be beneficial to improving the permeability of materials, and obviously, the continuous application of the red liquid is very remarkable in the effects of energy conservation, consumption reduction and water conservation and quality improvement, and is beneficial to further reducing the concentration cost and the water consumption.
Example 3: experiment of effect of regeneration and reuse of potassium hydroxide and acidification of bamboo pulp and sulfur dioxide by potassium hydroxide method
Test one: adding 200g (folded hundred) of moso bamboo chips, 28g of potassium hydroxide and 1000ml of water into a boiling pot, keeping the temperature at 120 ℃ and boiling for 4 hours, carrying out solid-liquid separation after boiling, fluffing, pulping, pulp screening, fiber dissociation and papermaking on the boiled bamboo, wherein the yield of the air-dried pulp is 69.2%, the residual alkali of black liquor is 4.82g/L, the beating degree is 40 DEG SR, and the paper ration is 80g/m 2.
And (2) testing II: introducing sulfur dioxide into the mixture of the black liquor and the slurry after fluffing and pulping to adjust the pH to about 4, obtaining a lignin-modified unbleached pulp and a mixed solution containing potassium sulfite and potassium hydrogen sulfite which are uniformly precipitated and adsorbed on the surface of unbleached pulp, adding 37g of calcium hydroxide into the solution obtained by filtering and washing, stirring for at least 60min, separating the potassium hydroxide solution regenerated by double decomposition reaction from the calcium sulfite precipitate again, supplementing the required amount of potassium hydroxide into the regenerated potassium hydroxide solution, adding 200g (folded hundred) of next batch of moso bamboo chips into a digester, preserving heat and boiling for 4h at 120 ℃, testing the residual alkali content after boiling, and repeating the operation to continuously apply the process for boiling the next batch of materials.
And (3) test III: adding 200g of moso bamboo chips (folded hundred) into a digester, adding 11.9g of dried calcium sulfite precipitate separated from the second test, introducing 6.4g of sulfur dioxide, adding 4g of concentrated sulfuric acid to adjust the pH to about 1.5, soaking and boiling in the temperature range of 120-130 ℃ and the time of 2.5-3 h, taking out the bamboo chips after cooling after boiling, kneading, pulping, screening pulp, dissociating fibers, filtering and drying, and calculating the pulp yield. The beating degree is controlled to be 40 DEG SR, the paper ration is 80g/m 2, and the mechanical property is tested by papermaking.
Table 5 results of test of quality of paper sample product by potassium method
Table 6 Potassium Process, black liquor test results for Potassium hydroxide regeneration
TABLE 7 test results of the performance and quality of pulping and papermaking of calcium bisulfate prepared by precipitation of calcium sulfite produced by regeneration of potassium hydroxide
The test shows that: the black liquor of the potassium method can be acidified and separated into lignin and potassium sulfite by using sulfurous acid or sulfur dioxide, the potassium hydroxide can be regenerated by double decomposition of lime and potassium sulfite/potassium hydrogen sulfite solution, and the potassium hydroxide after the loss is supplemented can be continuously used for digestion, thus proving that the method for acidifying and regenerating the potassium hydroxide by using the sulfur dioxide/sulfurous acid solution is completely feasible! And the yield of air-dried pulp is increased along with the increase of the application times, the quality of pulp paper after the application is close, the solid content of black liquor is increased along with the increase of the application times, and the produced calcium sulfite is completely feasible as a raw material for pulping by an acid method.
Example 4: evaluation of pulping effect of different plant materials by calcium bisulfate method
Test one: adding phyllostachys pubescens slices, giant fungus grass slices of 'oasis number one', rice straw and arundo donax into a digester respectively, folding up to 200g, adding 1000ml of calcium bisulfate splitting agent aqueous solution, wherein the dosage of the calcium bisulfate is 20g, adjusting the pH to about 1.5 by 4g of concentrated sulfuric acid, carrying out heat preservation and cooking for 2-3h at 120 ℃, taking out softened materials for kneading after the cooking is completed, pulping, screening pulp, carrying out fiber dissociation, filtering and drying, and calculating the pulp yield. The beating degree is controlled to be 40 DEG SR, the paper ration is 80g/m 2, and the mechanical property is tested by papermaking.
And (2) testing II: adding 200g of cotton stalk/reed stalk (folded hundred), 28g of potassium hydroxide and 1000ml of water into a boiling pot, keeping the temperature at 120 ℃ and boiling for 3 hours, carrying out solid-liquid separation after boiling, fluffing the boiled materials, pulping, screening pulp, dissociating fibers, filtering and drying, and calculating the pulp yield. The beating degree is controlled to be 40 DEG SR, paper is made, the paper ration is 80g/m 2, and the mechanical property is tested.
TABLE 8 yield of pulping of different plant Material with calcium Hydrogen sulfite or Potassium hydroxide and pulp Properties
The experimental results show that: in Table 8, raw materials such as phyllostachys pubescens, first-oasis fungus grass, rice straw, arundo donax, reed straw, cotton stalk and the like are steamed for 2-3 hours in a calcium bisulfate solution with pH value of 1.5, wherein the yield of air-dried pulp of the first-oasis fungus grass is 98.7%, the ring crush index of the prepared paper is 7.4 N.m/g, and the AA grade of a transverse ring crush index superior product required in GB/T13023-2008 is achieved.
Claims (10)
1. A process for producing a substance-based water-soluble fertilizer by coupling pulping by an acid method and pulping by an alkali method is characterized in that the pulping by the alkali method is to use a solution containing potassium hydroxide or sodium hydroxide as a resolving agent, the pulping by the acid method is to use a solution containing sulfuric acid and calcium bisulfide as a resolving agent, the pulping by the alkali method is to obtain black liquor, unbleached pulp or a mixture of the black liquor and unbleached pulp, the unbleached pulp and the unbleached pulp are acidified by sulfur dioxide or sulfurous acid solution to obtain unbleached pulp rich in lignin and water-soluble sulfite, the filtrate obtained by filtering the unbleached pulp is subjected to causticization conversion by slaked lime to filter calcium sulfite, the regenerated potassium hydroxide or sodium hydroxide filtrate is circularly used for pulping by the alkali method under the condition of supplementing the lost alkali amount, the filtered or simply separated filter residue rich in calcium sulfite is added into an aqueous solution, sulfur dioxide is introduced or the sulfuric acid solution is added for acidification and dissolution into the aqueous solution of calcium bisulfide, and the mixture is used for pulping by the acid method; wherein,
The acid pulping process comprises the following steps: soaking and boiling plant raw materials in a solution containing sulfuric acid and calcium bisulfide, and then kneading, pulping, filtering, washing and filtering to obtain unbleached pulp and pulping red liquor, wherein the solid-to-liquid ratio of the plant raw materials to the calcium bisulfide solution is 1:3-10 according to the absolute dry mass, the dosage of the calcium bisulfide in the calcium bisulfide solution is 5-15% of the absolute dry plant mass, the pH value of the calcium bisulfide solution is 1-5, the soaking and boiling temperature is 80-130 ℃, and the boiling time is 2-6h;
supplementing calcium sulfite into pulping red liquor filtered in the acid pulping process, adding sulfur dioxide or adding a sulfurous acid solution for acidification, then, circularly using the pulping red liquor, after nearly saturation of the circularly using, neutralizing and co-producing a bio-based water-soluble fertilizer raw material or fertilizer product which mainly contains calcium lignosulfonate, or directly using the partially extracted red liquor as a liquid fertilizer after neutralization and dilution, or separating precipitated calcium sulfate after adding potassium sulfate or ammonium sulfate into the red liquor to obtain a potassium lignosulfonate or ammonium lignosulfonate solution, and directly using the solution as a fertilizer after neutralization and pH adjustment of 6-8 or concentrating the solution into a liquid fertilizer or a powder water-soluble fertilizer product;
The alkaline pulping process comprises the following steps: soaking and boiling plant materials in a solution containing potassium hydroxide or sodium hydroxide, kneading and pulping to obtain a mixture of unbleached pulp and black liquor, introducing sulfur dioxide or adding an aqueous solution of sulfurous acid to acidify to pH 1-5, filtering, separating and washing to obtain unbleached pulp and filtrate which are rich in lignin, wherein the main component of the filtrate is potassium sulfite or sodium sulfite, adding lime or slaked lime pulp into the filtrate to stir and mix, precipitating, then applying supernatant containing potassium hydroxide or sodium hydroxide or filtrate as a resolving agent of an alkaline pulping process to pulp in the next batch, circularly applying a near-saturated solution, producing a solid fertilizer or a liquid fertilizer product of water-soluble lignin potassium by adjusting the pH, mixing the precipitated and separated calcium sulfite solid with a red liquid of an acid pulping process, introducing sulfur dioxide or adding the aqueous solution of sulfurous acid to acidify to pH 1-5, dissolving and converting the calcium sulfite into a calcium sulfite solution with strong water solubility, and applying the calcium sulfite as a resolving agent to the acid pulping process, and circularly saturating to obtain a water-soluble raw material or liquid fertilizer product which is rich in lignin calcium sulfonate.
2. The process according to claim 1, characterized in that the pulping red liquor is finally supplemented with calcium sulphite in an amount of 5-15% of the absolute dry plant mass.
3. A process according to any one of claims 1-2, characterized in that the solution is acidified to a pH of 3-5 by passing in sulphur dioxide or by adding an aqueous solution of sulphite.
4. The process according to any one of claims 1-2, characterized in that the sulphur dioxide is sulphur dioxide obtained by decomposition of calcium sulphite, or by high temperature reduction of desulphurized gypsum, phosphogypsum or fluorgypsum or natural gypsum in a kiln, or by incineration of sulphur, lime is lime obtained by decomposition of calcium sulphite, or lime obtained by high temperature reduction of desulphurized gypsum, phosphogypsum or fluorgypsum or natural gypsum in a kiln.
5. The process according to any one of claims 1-2, characterized in that the plant material is one or more of bamboo, fungus grass, arundo donax, reed, crop straw, bagasse, coconut shell bamboo processing residues.
6. The process of claim 5, wherein the crop straw is one or more of wheat, rice, corn, soybean, sorghum, cotton straw.
7. The process of claim 5 wherein the plant material is bamboo.
8. The process of claim 7 wherein the bamboo is crushed bamboo.
9. The process according to claim 5, wherein the plant material is one or more of bamboo, grass, arundo donax, crop straw, reed.
10. A method for synthesizing high-yield unbleached pulp and fertilizer rich in potassium lignin, calcium lignosulfonate and/or potassium lignosulfonate, which comprises the following steps:
soaking and boiling plant raw materials in a solution containing sulfuric acid and calcium bisulfide, and then rubbing, pulping and filtering to obtain unbleached pulp and red liquor, wherein the solid-to-liquid ratio of the plant raw materials to the calcium bisulfide solution is 1:3-10 according to the absolute dry mass, the dosage of the calcium bisulfide in the calcium bisulfide solution is 5-15% of the absolute dry plant mass, the pH value of the calcium bisulfide solution is regulated to be 1-5 by sulfuric acid, the soaking and boiling temperature is 80-130 ℃, and the boiling time is 2-6h;
Soaking and boiling plant materials in alkaline potassium hydroxide solution, kneading, pulping, filtering to obtain unbleached pulp and black liquor, mixing red liquor and black liquor, neutralizing, and filtering to separate fertilizer materials or fertilizer products containing calcium sulfite and rich in potassium lignin, potassium lignin sulfonate and calcium lignin sulfonate.
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| US4005060A (en) * | 1974-01-11 | 1977-01-25 | Skogsagarnas Industri Aktiebolag | Method, applied in the production of tall oil, of preventing or reducing the emission of odorous sulphur compounds and/or acid sulphur combustion products from the black liquor recovery process in alkaline pulping |
| CN102604120A (en) * | 2012-02-29 | 2012-07-25 | 福州大学 | Method for preparing lignin sulfonate dispersing agent by using two-step oxidization method |
| CN103510418A (en) * | 2012-06-25 | 2014-01-15 | 北京英力生科新材料技术有限公司 | New process for black liquor free chemical preparation of pulp |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101768887B (en) * | 2010-03-17 | 2012-12-26 | 山东和润浆纸有限公司 | Circular utilization method of straw in pulping and papermaking processes |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4005060A (en) * | 1974-01-11 | 1977-01-25 | Skogsagarnas Industri Aktiebolag | Method, applied in the production of tall oil, of preventing or reducing the emission of odorous sulphur compounds and/or acid sulphur combustion products from the black liquor recovery process in alkaline pulping |
| CN102604120A (en) * | 2012-02-29 | 2012-07-25 | 福州大学 | Method for preparing lignin sulfonate dispersing agent by using two-step oxidization method |
| CN103510418A (en) * | 2012-06-25 | 2014-01-15 | 北京英力生科新材料技术有限公司 | New process for black liquor free chemical preparation of pulp |
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