CN1137182C - Process for preparing disperser by improving lignin - Google Patents
Process for preparing disperser by improving lignin Download PDFInfo
- Publication number
- CN1137182C CN1137182C CNB001310054A CN00131005A CN1137182C CN 1137182 C CN1137182 C CN 1137182C CN B001310054 A CNB001310054 A CN B001310054A CN 00131005 A CN00131005 A CN 00131005A CN 1137182 C CN1137182 C CN 1137182C
- Authority
- CN
- China
- Prior art keywords
- xylogen
- electrooxidation
- lignin
- sulphite
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 229920005610 lignin Polymers 0.000 title claims abstract description 27
- 238000004519 manufacturing process Methods 0.000 title 1
- 238000006056 electrooxidation reaction Methods 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 19
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 claims abstract description 9
- 239000003513 alkali Substances 0.000 claims description 8
- YADSGOSSYOOKMP-UHFFFAOYSA-N lead dioxide Inorganic materials O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 239000002585 base Substances 0.000 claims description 4
- 238000007069 methylation reaction Methods 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 239000004033 plastic Substances 0.000 claims description 3
- 229920003023 plastic Polymers 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 102000004190 Enzymes Human genes 0.000 claims description 2
- 108090000790 Enzymes Proteins 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000000919 ceramic Substances 0.000 claims description 2
- GRWZHXKQBITJKP-UHFFFAOYSA-N dithionous acid Chemical compound OS(=O)S(O)=O GRWZHXKQBITJKP-UHFFFAOYSA-N 0.000 claims description 2
- 238000007772 electroless plating Methods 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 239000011133 lead Substances 0.000 claims description 2
- 239000012982 microporous membrane Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 239000010935 stainless steel Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 239000004568 cement Substances 0.000 abstract description 5
- 238000002360 preparation method Methods 0.000 abstract description 4
- 230000004048 modification Effects 0.000 abstract description 2
- 238000012986 modification Methods 0.000 abstract description 2
- 239000002270 dispersing agent Substances 0.000 abstract 2
- 230000002349 favourable effect Effects 0.000 abstract 1
- 239000006185 dispersion Substances 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 6
- 229920005552 sodium lignosulfonate Polymers 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- FOGYNLXERPKEGN-UHFFFAOYSA-N 3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfopropyl)phenoxy]propane-1-sulfonic acid Chemical compound COC1=CC=CC(CC(CS(O)(=O)=O)OC=2C(=CC(CCCS(O)(=O)=O)=CC=2)OC)=C1O FOGYNLXERPKEGN-UHFFFAOYSA-N 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical class [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 150000002500 ions Chemical group 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
Landscapes
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
The present invention relates to a preparation method for dispersing agents by the modification of lignin, and a physically and chemically combined method of electrooxidation and sulfomethylation is adopted in the present invention. The preparation method comprises the following steps: firstly, a direct current voltage of 2 to 12 volts is applied to a lignin solution of which the pH value is from 2 to 12, and the electrooxidation is carried out at the temperature of 10 to 40 DEG C; secondly, formaldehyde and sulfites are added into the lignin processed by the electrooxidation to carrying out reactions for 1 to 5 hours at 100 to 175 DEG C, and sulfomethylation reactions are then carried out. The method has the characteristics of mild reaction condition, no generation of public hazard and favorable dispersing performance of products, and the products can be used as the dispersing agent for dye, cement and other aqueous dispersing systems.
Description
The invention belongs to the method for preparing disperser by improving lignin, especially adopt electrooxidation and sulfomethylation to prepare the method for xylogen dispersion agent.
Xylogen is that nature is only second to the organic resource of the abundantest cellulosic recyclability, and annual China just surpasses 6,000,000 tons from the industrial lignin of paper industry, does not also have plant-scale reasonable utilization so far.Woodenly have many purposes, for example make tackiness agent, dispersion agent, tensio-active agent and be degraded to low molecular product etc., what prospect should be arranged is to make dispersion agent but at present tool is potential.Alkali lignin or vitriol xylogen (being referred to as alkali lignin) are class industrial lignins of output maximum in China, and this class xylogen lacks hydrophilic radical.Need could dissolve under alkaline condition, dispersed activity can be also very low, and industrial use is seldom arranged, and increase the dispersing property of this class xylogen, generally will be by complicated method of modifying.
The purpose of this invention is to provide a kind of method with preparing disperser by improving lignin, this method has the reaction conditions gentleness, does not produce public hazards, and the good characteristics of product dispersing property.
Preparation method provided by the invention adopts physics and chemofacies bonded electrooxidation and sulfomethylation method, and it specifically may further comprise the steps:
(1), the electrooxidation of xylogen: with lignin liquor perfectly straight stream voltage 2-12 volt in electrolyzer of pH value 2-12 with anode and negative electrode, carry out electrooxidation under temperature 10-40 ℃, the electric weight Q that control unit mass xylogen consumes in the reaction, the Q value is 5-25 kil. ocoulomb human relations/gram, wherein
Q=It/1000G (kil. ocoulomb human relations/gram)
In the formula: I is strength of current (ampere), and t is reaction times (second), and G is xylogen quality (gram);
(2), through the sulfomethylated lignin methylation reaction of electrooxidation: weight concentration be 20~30% in the lignin liquor of electrooxidation, add formaldehyde and sulphite, the mol ratio of xylogen and formaldehyde and sulphite is 1: 0.8-1.2: 1-3, reacted 1-5 hour down at 100-175 ℃.
Xylogen provided by the present invention both can be alkali lignin, vitriol xylogen, solvent xylogen, also can be the acid system xylogen, the enzyme process xylogen.
Anode can be through electroless plating and electroplate the plastic microporous membrane electrode of plumbic oxide in the xylogen electrooxidation, can also be platinum, gold and plate lead dioxide electrode on titanium base or ceramic base; Negative electrode can be a stainless steel, can also be lead, iron, nickel and carbon etc.
Sulphite is water miscible sulphite of a class and hydrosulphite in the sulfomethylated lignin methylation reaction of electrooxidation.
The xylogen electro-oxidation process is the process of a complexity, and its existing transfer transport has mass transfer in liquid phase and chemical reaction to combine again, wherein the most important thing is transfer transport.When xylogen (code name is RH) when carrying out electrooxidation, the result of transfer transport can form active negative ions group:
When the control appropriate reaction conditions, can make reaction based on oxidizing reaction, change the structure of xylogen and in lignin molecule, introduce more hydrophilic carboxyl by oxidizing reaction, thereby improve its dispersing property.
Electrooxidation method provided by the invention has been compared following advantage with chemical oxidization method:
1. the oxygenant that can not need other;
2. reaction is reaction nuisanceless, cleaning;
3. reaction conditions relaxes, and does not need high temperature, high pressure.
The xylogen dispersion agent of method preparation provided by the present invention has good dispersing property, can make dispersion agent and other dispersion system of dyestuff and cement.
Embodiment 1
The alkali lignin solution pH value of 8% concentration is transferred to 10.5, solution is joined in the special reactor with positive and negative electrode, the anode of this reactor is a titanium net plating plumbic oxide membrane electrode, negative electrode is 300 purpose stainless (steel) wires, add 5 volts in direct current then, temperature of reaction is 20 ℃, when every gram xylogen current consumption reaches 12 kil. ocoulomb human relations, stops electro-oxidation reaction.Alkali lignin through electrooxidation, per 1 mol alkali xylogen adds 1 mole in the formaldehyde of 37% concentration, 1.7 moles of S-WATs, 140 ℃ of reactions 2.5 hours, the modification alkali lignin product that obtains has good dispersing property to cement, mixes 0.5% this product in cement, cement flows is 260mm, and that do not have electrooxidation is 140mm.
Embodiment 2
The lignosulfonic acid sodium solution of 6% concentration, pH value is transferred to 12, this solution is poured in the special reactor, the anode of this reactor is that the plastics of plating plumbic oxide cross the nethike embrane electrode, negative electrode is 300 purpose stainless (steel) wire electrodes, adds galvanic current during reaction and presses 3 volts, 30 ℃ of temperature of reaction, when reaction reaches every gram sodium lignosulfonate current consumption 5 kil. ocoulomb human relations, stop electro-oxidation reaction.Through the sodium lignosulfonate of electrooxidation, per 1 mole of sodium lignosulfonate adds 0.8 mole of the formaldehyde solution of 37% concentration, 2 moles of sodium bisulfites, and solution pH value 10 is 165 ℃ of reactions 2 hours down.The modified lignin resin sodium sulfonate that obtains has high dispersing property, measures with Manganse Dioxide-potassium permanganate process, and dispersion energy is 314mg/100ml, is 236mg/100ml and there is not the sodium lignosulfonate dispersion energy through electrooxidation.
Claims (4)
1, a kind of method of preparing disperser by improving lignin adopts electrooxidation and sulfomethylation method, and it specifically may further comprise the steps:
(1), the electrooxidation of xylogen: with lignin liquor perfectly straight stream voltage 2-12 volt in electrolyzer of pH value 2-12 with anode and negative electrode, carry out electrooxidation under temperature 10-40 ℃, the electric weight Q that control unit mass xylogen consumes in the reaction, the Q value is 5-25 kil. ocoulomb human relations/gram, wherein, Q=It/1000G, unit is kil. ocoulomb human relations/gram, in the formula: I is a strength of current, and unit is an ampere; T is the reaction times, and unit is second; G is the xylogen quality, and unit is a gram;
(2), through the sulfomethylated lignin methylation reaction of electrooxidation: weight concentration be 20~30% in the lignin liquor of electrooxidation, add formaldehyde and sulphite, wherein the mol ratio of xylogen and formaldehyde and sulphite is 1: 0.8-1.2: 1-3, reacted 1-5 hour down at 100-175 ℃.
2,, it is characterized in that described xylogen is selected from alkali lignin, vitriol xylogen, solvent xylogen, acid system xylogen and enzyme process xylogen according to the method described in the claim 1.
3,, it is characterized in that anode in the described xylogen electrooxidation is selected from through electroless plating and electroplates plastic microporous membrane electrode, platinum, the gold of plumbic oxide and plate lead dioxide electrode on titanium base or ceramic base according to the method described in claim 1 or 2; Negative electrode is selected from stainless steel, lead, iron, nickel and carbon.
4, according to the method described in claim 1 or 2, it is characterized in that described in the sulfomethylated lignin methylation reaction of electrooxidation sulphite be selected from water miscible sulphite and hydrosulphite.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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CNB001310054A CN1137182C (en) | 2000-12-27 | 2000-12-27 | Process for preparing disperser by improving lignin |
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CNB001310054A CN1137182C (en) | 2000-12-27 | 2000-12-27 | Process for preparing disperser by improving lignin |
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CN1306026A CN1306026A (en) | 2001-08-01 |
CN1137182C true CN1137182C (en) | 2004-02-04 |
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CNB001310054A Expired - Fee Related CN1137182C (en) | 2000-12-27 | 2000-12-27 | Process for preparing disperser by improving lignin |
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Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102277591B (en) * | 2011-08-02 | 2014-03-05 | 北京化工大学 | Method for electrochemically degrading lignin |
CN103131020B (en) * | 2013-01-22 | 2015-04-22 | 华南理工大学 | Carboxylic sulfonic-acid-group lignin dye dispersing agent and preparation method thereof |
CN104062332A (en) * | 2014-06-30 | 2014-09-24 | 浙江天能电池(江苏)有限公司 | Determination method for lignosulfonic acid sodium salt capacity for resisting to electrochemical oxidation |
CN104532284A (en) * | 2014-12-16 | 2015-04-22 | 广西科技大学 | Converting method and converting device of lignocellulose in ionic solution through electrooxidation-hydrothermal method |
CN110483806A (en) * | 2018-05-15 | 2019-11-22 | 上海昶法新材料有限公司 | A kind of lignosulphonates and preparation method thereof |
CN110483805A (en) * | 2018-05-15 | 2019-11-22 | 上海昶法新材料有限公司 | A method of preparing lignosulphonates |
CN115746330B (en) * | 2022-11-08 | 2024-02-20 | 安徽成弘建新材料有限公司 | Modified alkali lignin, preparation method thereof, semi-coke grinding aid and use method thereof |
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