CN102441339B - Dissolving pulp sodium lignosulfonate dispersant, and reducing preparation method and application thereof - Google Patents
Dissolving pulp sodium lignosulfonate dispersant, and reducing preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a dissolving pulp sodium lignosulfonate dispersant, and a reducing preparation method and application thereof. Based on a concentrated dissolving pulp waste liquid, the lignose activity is improved under the action of a catalyst, then subjected to sulfomethylation reaction, subjected to reducing reaction to obtain a brownish-black or dark brown liquid, and subjected to spray drying to obtain a dark brown or nut-brown powdered sodium lignosulfonate dispersant, wherein the weight-average molecular weight Mw is 6000-40000, and the number-average molecular weight Mn is 3000-20000. The product can be widely used for concrete admixtures, dye dispersants and coal water slurry additives; each property of the product can meet the related quality standard requirements; and the product has the advantages of simple preparation process, moderate conditions, conventional equipment, low production cost and no emission of three wastes in the production process, and can achieve the purpose of changing wastes into valuables, thereby having popularization and application values.
Description
Technical field
The invention belongs to fine chemistry industry, environment-friendly material and dispersant field, particularly a kind of dissolving pulp sodium lignin sulfonate dispersant and reducing preparation method and application.
Background technology
Dissolving pulp claims again spoelalty pulp, or refined stock, its main application is to make to produce the viscose rayon of textile raw material, and it also is the raw material of the products such as glassine paper, pharmaceuticals industry sterilising filtration paper, acetate fiber, nitrocellulose, acid methyl cellulose, microcrystalline cellulose, cellulose ether.The common available masson pine of dissolving pulp, Eucalyptus, toothed oak wood, poplar, birch production, bamboo also can be used as the raw material of producing dissolving pulp.China is weaving big country, and output occupies the first in the world, along with the high speed development of textile industry, has also aggravated the demand contradictory of each fibrid raw material simultaneously, and particularly the petrochemicals as chemical fibre raw material are in short supply especially.The continuous rise of in short supply, the price of petrochemicals is of overall importance and long-term on the impact of textile industry, concerning Industrial Security and sustainable development.In order fundamentally to solve shortage and even the exhausted severe situation of " petrochemical industry resource ", it is biomass engineering innovation material, the new forms of energy of main body that each developed country of the world researches and develops the agricultural resources such as reproducible corn, soybean, sweet potato, straw pavilion and fast-growing woods just strategically with all strength.Under this background, for the development as the viscose rayon of textile raw material has brought opportunity, also brought opportunity for the development of producing dissolving pulp with fast growing wood.
Produce dissolving pulp two kinds of processes are arranged: prehydrolytic sulfate process and sulphite process.In general, the raw material that hemicellulose level is low can adopt acid sulfite process; If the raw material that resin content is high then must adopt prehydrolytic sulfate process.These two kinds of processes except producing the materials such as a small amount of reduced sugar, hemicellulose, have also produced a large amount of xylogen by-products when producing dissolving pulp.Sulphite process dissolving pulp waste liquid is mainly directly prepared lignosulfonates by concentrated, modification; Prehydrolytic sulfate process dissolving pulp waste liquid then reclaims employed alkali in the dissolving pulp production process by concentrated, causticization, and the method has caused the huge waste of this renewable resource of lignin.Based on this, how effectively to make good use of the lignin in the prehydrolytic sulfate process dissolving pulp waste liquid, improve the focus that its added value had become researcher research already.
Lignin is the unique non-oil renewable resource that aryl compound can be provided of nature, and it and cellulose, hemicellulose are the main components that consists of the plant skeleton, and its content in land plant is only second to cellulose, is second largest natural organic matter.Estimate that the whole world can produce 1,500 hundred million tons of lignin by plant growth every year, a large amount of use lignin can reduce the utilization to non-renewable resources such as coal, oil, natural gases as the raw material of chemical products, alleviates the crisis of non-renewable resources.It is reported that lignin can be used for producing concrete admixture, slurries additive agent, dispersant, adhesive, water treatment agent, adsorbent, phenolic resins and thinner etc., is the renewable raw material of a lot of chemical products.
Lack strongly hydrophilic functional group in the lignin molecule, the high activity position that can react simultaneously is not enough, so it is water-soluble and chemical reactivity is bad, has limited the range of application and the practical value that reclaim lignin.By the physical and chemical modified method, in lignin structure, introduce the high activity group, optimize the structural behaviour of lignin, improve the using value of its product, become lignin recovery and utilized the focus of studying.At present, the research and development about the modified lignin resin product both at home and abroad mainly concentrate on lignosulfonates (such as sodium lignin sulfonate, calcium lignosulfonate, magnesium lignosulfonate, ammonium lignosulphonate etc.), (US 4551151 to have studied the lower sulfonating reaction with lignin at 130～175 ℃ of formaldehyde and sodium sulfite such as Dilling Peter, 1985), he also utilizes the concentrated acid sulfonation lignin to make lignosulfonates, and (US 4740590,1988), he also utilizes SO
2Lignosulfonate is prepared the low sodium lignin sulfonate of salt content (US 5049661,1991); Erich Adler etc. utilizes formaldehyde and sodium sulfite that lignin is carried out the high temperature sulfonation under 100～170 ℃ and prepares sodium lignin sulfonate (US 2680113,1954); After the black digestion liquid classification of Forss Bengt with sodium base bisulfite pulping, be prepared into lignosulfonates as concrete admixture (US 4450106,1984) through sulfonating reaction; Ishitoku Hideaki etc. prepare sodium lignin sulfonate (US 5811527,1998) again with the black liquor of pulp making acidifying, after precipitating and isolating lignin; Liu Minghua etc. utilize black liquor of pulp making under the condition of catalyst, the low-temperature sulfonation lignin makes sodium lignin sulfonate (CN 1704372A, 2005), he also by black liquid is carried out catalytic oxidation, sulfomethylation prepares sodium lignin sulfonate dispersant (CN 102153764A, 2011), he also utilizes the ground wood pulp waste liquid to carry out etherificate, sulfonation, the synthetic lignin sulfonic acid product salt (CN 102146164A, 2011) of condensation reaction; Wei Handao etc. first with lignin 10～40 ℃ of electroxidation, add again formaldehyde and sulphite and carry out sulfomethylation at 100～175 ℃ and prepare lignin sulfonic acid dipersant (CN 1306026A, 2001); Qiu Xueqing etc. utilize lignin, phenol, aminobenzenesulfonic acid and formaldehyde to synthesize lignin modification sulfamate high-effective water-reducing agent (CN 101157531A, 2008), he also utilizes lignin adding aldehyde compound and sulfonating agent to make the sodium lignin sulfonate (CN 101475604A, 2009) of highly sulfonated under the microwave condition.
The dispersive property of Sulphonation of Lignin product is desirable not enough, and then has limited its extent of spreading amd application but generally speaking.Again because dissolving pulp waste liquid constituent is complicated, and has very strong penetrating odor.Therefore, utilize conventional method and above domestic and international research method, all can not well address these problems, provide a kind of reduction technique to prepare the method for sodium lignin sulfonate so the present invention is directed to such waste liquid, so not only can improve the combination property (such as molecular weight, late strength of concrete, fluidity, cement adaptability and temperature accommodation etc.) of product, remove simultaneously the penetrating odor of waste liquid, make the smell of product be tending towards gentle.So both can make dissolving pulp accessory substance lignin be able to higher value application, solve again the problem of environmental pollution of dissolving pulp waste liquid.
Summary of the invention
The object of the present invention is to provide a kind of dissolving pulp sodium lignin sulfonate dispersant and reducing preparation method and application, the method preparation technology is simple, mild condition, adopt conventional equipment, production cost low, and realize that change " giving up " is the purpose of " treasured ", and production process is discharged without " three wastes ", has application value.
For achieving the above object, the present invention adopts following technical scheme:
Sodium lignin sulfonate dispersant of the present invention is dark brown or dark-brown powder, its weight average molecular weight Mw is 6000～40000, number-average molecular weight Mn is 3000～20000, it is to utilize dissolving pulp waste liquid after concentrated to improve the activity of its lignin under the effect of catalyst, then carry out sulfomethylation, reduction reaction occuring at last get brownish black or dark brown liquid, obtains after spray-dried.
The reducing preparation method of dissolving pulp sodium lignin sulfonate dispersant may further comprise the steps: it is 20～60% that the dissolving pulp waste liquid is concentrated into solid content, adds catalyst, 40～130 ℃ of lower reaction 0.5～1.5h; Add the pH value to 10 of acid regulator regulation system～13, add sulfonating agent, aldehyde compound, water behind temperature adjustment to 80～160 ℃, react 2～5h; Then regulation system temperature to 60～130 ℃ add reducing agent and react 0.5～2h again and obtain brownish black or dark brown liquid, spray-dried dark brown or the pulverous sodium lignin sulfonate dispersant of dark-brown of obtaining; The mass percent of described each raw material is as follows:
Dissolving pulp waste liquid: 50～85%
Catalyst: 0.01～0.1%
Acid regulator: 1.3～5.2%
Sulfonating agent: 2～8.3%
Aldehyde compound: 1.8～8%
Reducing agent: 0.5～10%
Water: 2～28%.
Wherein said dissolving pulp waste liquid is one or more the mixture that is selected from bamboo, toothed oak wood, poplar, Eucalyptus, birch, the Chinese red pine dissolving pulp waste liquid; Described catalyst is one or more the composition in ferrous sulfate, ferrous nitrate, iron ammonium sulfate, copper sulphate, copper nitrate, cobaltous sulfate, cobalt nitrate, nickelous sulfate, the nickel nitrate; Described acid regulator is sulfuric acid, phosphoric acid, sulfamic acid, amino acid, to one or more the composition in sulfamic acid, p-methyl benzenesulfonic acid, gluconic acid, nicotinic acid, tartaric acid, citric acid, salicylic acid, butanedioic acid, maleic acid, the oxalic acid; Described sulfonating agent is one or more the composition in sodium sulfite, sodium hydrogensulfite, sulfanilic acid, sodium pyrosulfite, sodium isethionate, ammonium sulfite, ammonium bisulfite, the sulfamic acid; Described aldehyde compound is formaldehyde, acetaldehyde, glutaraldehyde, methacrylaldehyde, succinaldehyde, melamine formaldehyde (MF), metaformaldehyde, the composition of one or more in the paraformaldehyde; Described reducing agent is one or more the composition in sodium dithionite, thiourea dioxide, amino imino sulfonic acid, rongalite, ferrous gluconate, reduced sugar, sodium hydroxymethanesulfinate, inferior sodium phosphate, dihydroxyacetone (DHA), sodium borohydride, the cyclanone.
Sodium lignin sulfonate dispersant of the present invention is as concrete admixture, dye dispersant and slurries additive agent.
Remarkable advantage of the present invention and good effect are:
(1) the present invention carries out catalytic reaction to the dissolving pulp waste liquid after concentrated first, improve the activity of lignin in the dissolving pulp waste liquid, adopt again sulfomethylation technique, lignin molecule is sulfonated fully, pass through at last the further modified product of senior reduction technique, and effectively controlled molecular weight product.This product has the several functions such as dispersion, complexing, chelating, of many uses, can be used for the multiple fields such as cement water reducing agent, dye dispersant and slurries additive agent, and has an intermediate molecular weight, the advantages such as low content of reducing sugar and integrated performance index are good have not yet to see the relevant report of utilizing the reduction technique modified lignin resin.
(2) the present invention utilizes the dissolving pulp waste liquid to be raw material; through the reduction reaction modification; realized the higher value application to lignin; alleviated widely the crisis of non-renewable resources; and this product processes is simple, mild condition; adopt conventional equipment, production cost lower, greatly improved enterprise competitiveness.
(3) product application industry of the present invention is in extensive range, useful as concrete additive, dye dispersant and slurries additive agent etc., and product is nontoxic, uses and is not subjected to season and region limits, is convenient to transportation and storage.
(4) the present invention uses the direct catalysis of dissolving pulp waste liquid, sulfonation, reduction, need not reclaim lignin by acidification, and production process is without the discharging of " three wastes ", and has solved the dissolving pulp waste water pollution problem, be one clean, environmentally friendly technique.
The specific embodiment
Sodium lignin sulfonate dispersant of the present invention is dark brown or dark-brown powder, its weight average molecular weight Mw is 6000～40000, number-average molecular weight Mn is 3000～20000, it is to utilize dissolving pulp waste liquid after concentrated to improve the activity of its lignin under the effect of catalyst, then carry out sulfomethylation, reduction reaction occuring at last get brownish black or dark brown liquid, obtains after spray-dried.
The reducing preparation method of dissolving pulp sodium lignin sulfonate dispersant may further comprise the steps: it is 20～60% that the dissolving pulp waste liquid is concentrated into solid content, adds catalyst, 40～130 ℃ of lower reaction 0.5～1.5h; Add the pH value to 10 of acid regulator regulation system～13, add sulfonating agent, aldehyde compound, water behind temperature adjustment to 80～160 ℃, react 2～5h; Then regulation system temperature to 60～130 ℃ add reducing agent and react 0.5～2h again and obtain brownish black or dark brown liquid, spray-dried dark brown or the pulverous sodium lignin sulfonate dispersant of dark-brown of obtaining; The mass percent of described each raw material is as follows:
Dissolving pulp waste liquid: 50～85%
Catalyst: 0.01～0.1%
Acid regulator: 1.3～5.2%
Sulfonating agent: 2～8.3%
Aldehyde compound: 1.8～8%
Reducing agent: 0.5～10%
Water: 2～28%.
Wherein said dissolving pulp waste liquid is one or more the mixture that is selected from bamboo, toothed oak wood, poplar, Eucalyptus, birch, the Chinese red pine dissolving pulp waste liquid; Described catalyst is one or more the composition in ferrous sulfate, ferrous nitrate, iron ammonium sulfate, copper sulphate, copper nitrate, cobaltous sulfate, cobalt nitrate, nickelous sulfate, the nickel nitrate; Described acid regulator is sulfuric acid, phosphoric acid, sulfamic acid, amino acid, to one or more the composition in sulfamic acid, p-methyl benzenesulfonic acid, gluconic acid, nicotinic acid, tartaric acid, citric acid, salicylic acid, butanedioic acid, maleic acid, the oxalic acid; Described sulfonating agent is one or more the composition in sodium sulfite, sodium hydrogensulfite, sulfanilic acid, sodium pyrosulfite, sodium isethionate, ammonium sulfite, ammonium bisulfite, the sulfamic acid; Described aldehyde compound is formaldehyde, acetaldehyde, glutaraldehyde, methacrylaldehyde, succinaldehyde, melamine formaldehyde (MF), metaformaldehyde, the composition of one or more in the paraformaldehyde; Described reducing agent is one or more the composition in sodium dithionite, thiourea dioxide, amino imino sulfonic acid, rongalite, ferrous gluconate, reduced sugar, sodium hydroxymethanesulfinate, inferior sodium phosphate, dihydroxyacetone (DHA), sodium borohydride, the cyclanone.
Sodium lignin sulfonate dispersant of the present invention is as concrete admixture, dye dispersant and slurries additive agent.
Below in conjunction with specific embodiment the present invention is described in detail, but the present invention is not limited only to this.
Embodiment 1
(1) raw material and consumption
The dissolving pulp waste liquid of masson pine (solid content is 20%): 850.0 Kg
The mixture of ferrous sulfate and cobaltous sulfate (mass ratio is 9:1): 0.5 Kg
The mixture of phosphoric acid and gluconic acid (mass ratio is 2:3): 38.5 Kg
Sodium hydrogensulfite: 20.0 Kg
Formaldehyde: 55.9 Kg
Thiourea dioxide: 15.1 Kg
Water: 20.0 Kg
(2) processing step and parameter
It is 20% that the dissolving pulp waste liquid of masson pine is concentrated into solid content, takes out 850.0 Kg to reactor with pump, and adds the mixture of 0.5 Kg ferrous sulfate and cobaltous sulfate, reacts 1h under 60 ℃ temperature; The mixture that adds 38.5 Kg phosphoric acid and gluconic acid transfers to 10 with system pH, is warming up to 100 ℃, and adds the mixture reaction 4h of 20.0 Kg sodium hydrogensulfites, 55.9 Kg formaldehyde, 20.0 Kg water; Then system temperature is down to 90 ℃, adds 15.1 Kg thiourea dioxides, discharging behind the reaction 1h obtains the brownish black fluid product, the spray-dried dark-brown powdery product that obtains, and its weight average molecular weight Mw is 18000, number-average molecular weight Mn is 9000.
Embodiment 2
(1) raw material and consumption
The dissolving pulp waste liquid mixture of masson pine and birch (mass ratio is 3:2, solid content 26%): 844 Kg
The mixture of ferrous sulfate, copper sulphate and cobaltous sulfate (mass ratio is 7:2:1): 0.2 Kg
Sulfamic acid and amino acid whose mixture (mass ratio is 1:1): 23.5 Kg
The mixture of sodium hydrogensulfite and sodium sulfite (mass ratio is 2:1): 58.4 Kg
The mixture of formaldehyde and paraformaldehyde (mass ratio is 4:1): 18.0 Kg
The mixture of sodium dithionite and thiourea dioxide (mass ratio is 1:1): 5.0 Kg
Water: 50.9 Kg
(2) processing step and parameter
It is 26% that the dissolving pulp waste liquid mixture of masson pine and birch is concentrated into solid content, takes out 844.0 Kg to reactor with pump, and adds the mixture of 0.2 Kg ferrous sulfate, copper sulphate and cobaltous sulfate, reacts 1h under 70 ℃ temperature; Add 23.5 Kg sulfamic acids and amino acid whose mixture system pH is transferred to 12, be warming up to 160 ℃, and add the mixture of mixture, 18.0 Kg formaldehyde and the paraformaldehyde of 58.4 Kg sodium hydrogensulfites and sodium sulfite, the mixture reaction 3h of 45.9 Kg water; Then system temperature is down to 70 ℃, adds the mixture of 5.0 Kg sodium dithionites and thiourea dioxide, discharging behind the reaction 2h, obtain the dark brown fluid product, the spray-dried dark brown powdery product that obtains, its weight average molecular weight Mw is 19000, number-average molecular weight Mn is 9500.
Embodiment 3
(1) raw material and consumption
The dissolving pulp waste liquid of bamboo (solid content 35%): 757.0 Kg
The mixture of ferrous nitrate and cobalt nitrate (mass ratio is 9:1): 0.1 Kg
Mixture (mass ratio is 1:2) to sulfamic acid and citric acid: 40.8 Kg
Sodium pyrosulfite: 29.6 Kg
The mixture of formaldehyde and acetaldehyde (mass ratio is 4:1): 80.0 Kg
The mixture of sodium dithionite and amino imino sulfonic acid (mass ratio is 1:1): 26.8 Kg
Water: 65.7 Kg
(2) processing step and parameter
It is 35% that the dissolving pulp waste liquid of bamboo is concentrated into solid content, takes out 757.0 Kg to reactor with pump, and adds the mixture of 0.1 Kg ferrous nitrate and cobalt nitrate, reacts 0.5h under 130 ℃ temperature; Add 40.8 Kg the mixture of the citric acid of sulfamic acid is transferred to 11 with system pH, be warming up to 90 ℃, and add the mixture of the acetaldehyde of 29.6 Kg sodium pyrosulfites, 80.0 Kg formaldehyde, the mixture reaction 3.5h of 65.7 Kg water; Then system temperature is down to 60 ℃, adds the mixture of 26.8 Kg sodium dithionites and amino imino sulfonic acid, discharging behind the reaction 1.5h, obtain the brownish black fluid product, the spray-dried dark-brown powdery product that obtains, its weight average molecular weight Mw is 40000, number-average molecular weight Mn is 20000.
Embodiment 4
(1) raw material and consumption
The dissolving pulp waste liquid mixture of poplar and toothed oak wood (mass ratio is 1:1, solid content 40%): 809.0 Kg
The mixture of ferrous sulfate and nickelous sulfate (mass ratio is 9:1): 0.4 Kg
The mixture of the concentrated sulfuric acid and gluconic acid (mass ratio is 1:4): 13.0 Kg
The mixture of sodium hydrogensulfite and sodium isethionate (mass ratio is 3:1): 47.8 Kg
The mixture of formaldehyde and metaformaldehyde (mass ratio is 4:1): 46.2 Kg
The mixture of ferrous gluconate and reduced sugar (mass ratio is 1:1): 34.4 Kg
Water: 49.2 Kg
(2) processing step and parameter
It is 40% that the dissolving pulp waste liquid mixture of poplar and toothed oak wood is concentrated into solid content, takes out 809.0 Kg to reactor with pump, and adds the mixture of 0.4 Kg ferrous sulfate and nickelous sulfate, reacts 1.5h under 40 ℃ temperature; The mixture that adds the 13 Kg concentrated sulfuric acids and gluconic acid transfers to 13 with system pH, be warming up to 130 ℃, and add the mixture of mixture, 46.2 Kg formaldehyde and the metaformaldehyde of 47.8 Kg sodium hydrogensulfites and sodium isethionate, the mixture reaction 4h of 49.2 Kg water; Then system temperature is remained on 130 ℃, add the mixture of 34.4 Kg ferrous gluconates and reduced sugar, discharging behind the reaction 0.5h, obtain the dark brown fluid product, the spray-dried dark brown powdery product that obtains, its weight average molecular weight Mw is 30000, number-average molecular weight Mn is 15000.
Embodiment 5
(1) raw material and consumption
The dissolving pulp waste liquid mixture of Eucalyptus and toothed oak wood (mass ratio is 3:2, solid content 48%): 678.0 Kg
The mixture of ferrous nitrate and nickel nitrate (mass ratio is 9:1): 0.3 Kg
The mixture of maleic acid and oxalic acid (mass ratio is 1:1): 15.5 Kg
The mixture of sodium pyrosulfite and ammonium sulfite (mass ratio is 3:1): 83.0 Kg
The mixture of formaldehyde and glutaraldehyde (mass ratio is 4:1): 27.6 Kg
The mixture of dihydroxyacetone (DHA) and cyclanone (mass ratio is 1:1): 48.2 Kg
Water: 147.4 Kg
(2) processing step and parameter
It is 48% that the dissolving pulp waste liquid mixture of Eucalyptus and toothed oak wood is concentrated into solid content, takes out 678.0 Kg to reactor with pump, and adds the mixture of 0.3 Kg ferrous nitrate and nickel nitrate, reacts 0.5h under 80 ℃ temperature; The mixture that adds 15.5 Kg maleic acids and oxalic acid transfers to 12.5 with system pH, is incubated at 80 ℃, and adds the mixture of mixture, 27.6 Kg formaldehyde and the glutaraldehyde of 83 Kg sodium pyrosulfites and ammonium sulfite, the mixture reaction 5h of 147.4 Kg water; Then system temperature is down to 95 ℃, adds the mixture of 48.2 Kg dihydroxyacetone (DHA)s and cyclanone, discharging behind the reaction 0.5h, obtain the dark brown fluid product, the spray-dried dark brown powdery product that obtains, its weight average molecular weight Mw is 36000, number-average molecular weight Mn is 18000.
Embodiment 6
(1) raw material and consumption
The dissolving pulp waste liquid mixture of Eucalyptus and poplar (mass ratio is 1:1, solid content 48%): 647.0 Kg
The mixture of ferrous sulfate, sodium thiosulfate and vulcanized sodium (mass ratio is 3:1:1): 0.8 Kg
Gluconic acid: 21.8 Kg
The mixture of sodium pyrosulfite and sulfamic acid (mass ratio is 4:1): 66.1 Kg
Formaldehyde: 41.7 Kg
Sodium hydroxymethanesulfinate: 55.1 Kg
Water: 167.5 Kg
(2) processing step and parameter
It is 48% that the dissolving pulp waste liquid mixture of Eucalyptus and poplar is concentrated into solid content, takes out 647.0 Kg to reactor with pump, and adds the mixture of 0.8 Kg ferrous sulfate, sodium thiosulfate and vulcanized sodium, reacts 1.5h under 50 ℃ temperature; Add 21.8 Kg gluconic acids system pH is transferred to 10.5, be warming up to 160 ℃, and add mixture, the 41.7 Kg formaldehyde of 66.1 Kg sodium pyrosulfites and sulfamic acid, the mixture reaction 2h of 167.5 Kg water; Then system temperature is down to 120 ℃, adds 55.1 Kg sodium hydroxymethanesulfinates, discharging behind the reaction 2h obtains the dark brown fluid product, the spray-dried dark brown powdery product that obtains, and its weight average molecular weight Mw is 8000, number-average molecular weight Mn is 4000.
Embodiment 7
(1) raw material and consumption
The dissolving pulp waste liquid mixture of poplar and masson pine (mass ratio is 1:3, and solid content is 50%): 606.0Kg
The mixture of ferrous sulfate, copper sulphate and cobaltous sulfate (mass ratio is 7:2:1): 0.9 Kg
The mixture of sulfamic acid and oxalic acid (mass ratio is 1:1): 52.0 Kg
The mixture of sodium hydrogensulfite and ammonium bisulfite (mass ratio is 3:1): 32.3 Kg
The mixture of formaldehyde and methacrylaldehyde (mass ratio is 4:1): 48.5 Kg
The mixture of sodium dithionite and rongalite (mass ratio is 1:2): 71.3 Kg
Water: 189.0 Kg
(2) processing step and parameter
It is 50% that the dissolving pulp waste liquid mixture of poplar and masson pine is concentrated into solid content, takes out 606.0 Kg to reactor with pump, and adds the mixture of 0.9 Kg ferrous sulfate, copper sulphate and cobaltous sulfate, reacts 1h under 110 ℃ temperature; The mixture that adds 50.0 Kg sulfamic acids and oxalic acid transfers to 11 with system pH, be warming up to 140 ℃, and add the mixture of mixture, 50.5 Kg formaldehyde and the methacrylaldehyde of 32.3 Kg sodium hydrogensulfites and ammonium bisulfite, the mixture reaction 3.5h of 229.0 Kg water; Then system temperature is down to 85 ℃, adds the mixture of 31.3 Kg sodium dithionites and rongalite, discharging behind the reaction 1.5h, obtain the brownish black fluid product, the spray-dried dark-brown powdery product that obtains, its weight average molecular weight Mw is 28000, number-average molecular weight Mn is 14000.
Embodiment 8
(1) raw material and consumption
The dissolving pulp waste liquid of masson pine (solid content is 55%): 557.0 Kg
The mixture of ferrous nitrate, copper nitrate and cobalt nitrate (mass ratio is 7:2:1): 0.7 Kg
The mixture of gluconic acid and nicotinic acid (mass ratio is 3:1): 30.5 Kg
The mixture of sodium hydrogensulfite and sodium pyrosulfite (mass ratio is 1:1): 63.1 Kg
Formaldehyde: 42.7 Kg
Inferior sodium phosphate: 23.5 Kg
Water: 282.5 Kg
(2) processing step and parameter
It is 55% that the dissolving pulp waste liquid of splendid achnatherum is concentrated into solid content, takes out 557.0 Kg to reactor with pump, and adds the mixture of 0.7 Kg ferrous nitrate, copper nitrate and cobalt nitrate, reacts 1h under 90 ℃ temperature; The mixture that adds 30.5 Kg gluconic acids and nicotinic acid transfers to 11.5 with system pH, is warming up to 110 ℃, and adds mixture, the 42.7 Kg formaldehyde of 63.1 Kg sodium hydrogensulfites and sodium pyrosulfite, the mixture reaction 4h of 222.5 Kg water; Then system temperature is remained on 90 ℃, add 83.5 Kg inferior sodium phosphate, discharging behind the reaction 1h obtains the brownish black fluid product, the spray-dried dark-brown powdery product that obtains, and its weight average molecular weight Mw is 6000, number-average molecular weight Mn is 3000.
Embodiment 9
(1) raw material and consumption
The dissolving pulp waste liquid of bamboo (solid content is 60%): 500.0 Kg
The mixture of ferrous sulfate, cobaltous sulfate and nickelous sulfate (mass ratio is 8:1:1): 1.0 Kg
The mixture of phosphoric acid and sulfamic acid (mass ratio is 8:1:1): 26.9 Kg
The mixture of sodium sulfite, sodium hydrogensulfite and sodium pyrosulfite (mass ratio is 1:2:5): 54.3 Kg
The mixture of formaldehyde and paraformaldehyde (mass ratio is 4:1): 37.8 Kg
The mixture of sodium borohydride and rongalite (mass ratio is 1:1): 100.0 Kg
Water: 280.0 Kg
(2) processing step and parameter
It is 60% that the dissolving pulp waste liquid of bamboo is concentrated into solid content, takes out 500.0 Kg to reactor with pump, and adds the mixture of 1.0 Kg ferrous sulfate, cobaltous sulfate and nickelous sulfate, reacts 1h under 100 ℃ temperature; The mixture that adds 26.9 Kg phosphoric acid and sulfamic acid transfers to 12 with system pH, be warming up to 120 ℃, and add the mixture of mixture, 37.8 Kg formaldehyde and the paraformaldehyde of 54.3 Kg sodium sulfites, sodium hydrogensulfite and sodium pyrosulfite, the mixture reaction 4h of 338.0 Kg water; Then system temperature is down to 100 ℃, adds the mixture of 42.0 Kg sodium borohydrides and rongalite, discharging behind the reaction 0.5h, obtain the dark brown fluid product, the spray-dried dark brown powdery product that obtains, its weight average molecular weight Mw is 24000, number-average molecular weight Mn is 12000.
Embodiment 10
Performance test
(1) cement water reducing agent
Will be by raw material proportioning and the preparation-obtained sodium lignin sulfonate of processing step of above embodiment, measure respectively flowing degree of net paste of cement (with reference to GB GB/T-8077-2000-concrete admixture homogenieity test method, the ratio of mud is 0.35 during measurement, the water reducer volume is 0.25%), and with market on like product compare, as shown in table 1; Simultaneously embodiment 6 product section performance indications are tested, as shown in table 2.
(2) dye dispersant
Heat-resistant stability detects by HG/T 3399-2001 " mensuration of dye diffusion performance " and grades, such as table 3, shown in the table 4.
(3) slurries additive agent
Selecting the Shaanxi shenfu coal is research object, after fragmentation, ore grinding, screening and grating, add the moisture of amount of calculation and the sodium lignin sulfonate of embodiment 4 preparations, can obtain the water-coal-slurry of variable concentrations after stirring, utilize LV type Broookfield viscometer determining Cws Viscosity, and adopt the Rod drop test method to check the stability of water-coal-slurry.The size grading of coal: D(0.5)=22 μ m; D(0.9)=110 μ m;＜75 μ m=80%;＜5 μ m=20%; Average grain diameter=45 μ m.Shown in result such as the table 5, table 6.
Table 1 flowing degree of net paste of cement (mm of unit)
The partial properties index of table 2 embodiment 6 products
Table 3 dispersant of disperse dye is to the effect of 150 ℃ of heat-resistant stabilities of different disperse dyes
Under table 4 different temperatures dispersant of disperse dye to disperse dyes heat-resistant stability on effect
The pulping stability test of table 5 product
Annotate: embodiment 4 products are reinforced with liquid form, and chemical feeding quantity is 0.8%(take the quality of butt coal as benchmark), room temperature: 21.0-25.0 ℃.
Table 6 performance comparison test
Annotate: embodiment product 4 is reinforced with liquid form, and chemical feeding quantity is 0.8%; The acrylic acid series additive is reinforced with liquid form, and chemical feeding quantity is 1.0%; Naphthalene system, humic acid and three kinds of lignosulfonates are reinforced with solid form, chemical feeding quantity be respectively 0.8%, 1.0%, 1.0%, 1.0% and 1.0%(take the quality of butt coal as benchmark), room temperature: 23.6-29.2 ℃.
The above only is preferred embodiment of the present invention, and all equalizations of doing according to the present patent application claim change and modify, and all should belong to covering scope of the present invention.
Claims (1)
1. the reducing preparation method of a dissolving pulp sodium lignin sulfonate dispersant, it is characterized in that: the dissolving pulp waste liquid after utilization is concentrated improves the activity of its lignin under the effect of catalyst, then carry out sulfomethylation, reduction reaction occurs at last get brownish black or dark brown liquid, the pulverous sodium lignin sulfonate dispersant of the dark brown that obtains after spray-dried or dark-brown, its weight average molecular weight Mw is 6000～40000, number-average molecular weight Mn is 3000～20000, as concrete admixture, dye dispersant and slurries additive agent;
The preparation method may further comprise the steps: it is 20～60% that the dissolving pulp waste liquid is concentrated into solid content, adds catalyst, 40～130 ℃ of lower reaction 0.5～1.5h; Add the pH value to 10 of acid regulator regulation system～13, add sulfonating agent, aldehyde compound, water behind temperature adjustment to 80～160 ℃, react 2～5h; Then regulation system temperature to 60～130 ℃ add reducing agent and react 0.5～2h again and obtain brownish black or dark brown liquid, spray-dried dark brown or the pulverous sodium lignin sulfonate dispersant of dark-brown of obtaining; The mass percent of described each raw material is as follows:
Dissolving pulp waste liquid: 50～85%
Catalyst: 0.01～0.1%
Acid regulator: 1.3～5.2%
Sulfonating agent: 2～8.3%
Aldehyde compound: 1.8～8%
Reducing agent: 0.5～10%
Water: 2～28%;
Described dissolving pulp waste liquid is one or more the mixture that is selected from bamboo, toothed oak wood, poplar, Eucalyptus, birch, the Chinese red pine dissolving pulp waste liquid;
Described catalyst is one or more the composition in ferrous sulfate, ferrous nitrate, iron ammonium sulfate, copper sulphate, copper nitrate, cobaltous sulfate, cobalt nitrate, nickelous sulfate, the nickel nitrate;
Described acid regulator is sulfuric acid, phosphoric acid, sulfamic acid, amino acid, to one or more the composition in sulfamic acid, p-methyl benzenesulfonic acid, gluconic acid, nicotinic acid, tartaric acid, citric acid, salicylic acid, butanedioic acid, maleic acid, the oxalic acid;
Described sulfonating agent is one or more the composition in sodium sulfite, sodium hydrogensulfite, sulfanilic acid, sodium pyrosulfite, sodium isethionate, ammonium sulfite, ammonium bisulfite, the sulfamic acid;
Described aldehyde compound is formaldehyde, acetaldehyde, glutaraldehyde, methacrylaldehyde, succinaldehyde, melamine formaldehyde (MF), metaformaldehyde, the composition of one or more in the paraformaldehyde;
Described reducing agent is one or more the composition in sodium dithionite, thiourea dioxide, amino imino sulfonic acid, rongalite, ferrous gluconate, reduced sugar, sodium hydroxymethanesulfinate, inferior sodium phosphate, dihydroxyacetone (DHA), sodium borohydride, the cyclanone.
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| CN102838754B (en) * | 2012-09-18 | 2014-07-09 | 福州大学 | Method for preparing lignin-based ceramic additive through sulfomethylation and phosphorous hydroxylation |
| CN103588410A (en) * | 2013-11-01 | 2014-02-19 | 江苏百瑞吉新材料有限公司 | High efficiency water reducer prepared from paper pulp black liquor and preparation method thereof |
| CN104163925B (en) * | 2014-07-09 | 2016-10-05 | 华南理工大学 | A kind of Carboxylation alkali lignin sulfonate dye dispersant and preparation method thereof |
| CN104532641B (en) * | 2014-11-28 | 2017-03-01 | 武长安 | The energy-saving and environmental protection of Plant fiber, resource pulping process |
| CN104474966B (en) * | 2014-12-30 | 2017-02-22 | 福建清源科技有限公司 | Modified lignin-based dispersing agent and preparation method thereof |
| CN105418079B (en) * | 2015-10-29 | 2017-10-20 | 福州大学 | Biomass-based dispersant and its methods and applications are prepared using percolate |
| CN105541930B (en) * | 2015-12-16 | 2018-03-09 | 中铁十二局集团有限公司 | A kind of preparation method of glucose sulphonic acid ester |
| CN111218833A (en) * | 2020-04-01 | 2020-06-02 | 李孝亭 | Method for preventing accumulation of prehydrolysis liquid soluble lignin of sulfate dissolving pulp |
| CN112646101B (en) * | 2021-01-14 | 2022-04-08 | 福州大学 | Lignin degradation product-sulfonated acetone-formaldehyde polycondensate dispersant and preparation method thereof |
| CN114558880B (en) * | 2022-03-14 | 2024-04-16 | 武汉理工大学 | Surfactant suitable for dealkalization of red mud and dealkalization method of red mud |
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Application publication date: 20120509 Assignee: SANMING YUANFU BIOMASS TECHNOLOGY Co.,Ltd. Assignor: FUZHOU University Contract record no.: X2020980000765 Denomination of invention: Dissolving pulp sodium lignosulfonate dispersant, and reducing preparation method and application thereof Granted publication date: 20131030 License type: Exclusive License Record date: 20200317 |