CN1341568A - Modified lignin sulfonate multifunctional water treatment agent and its preparation method - Google Patents
Modified lignin sulfonate multifunctional water treatment agent and its preparation method Download PDFInfo
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- CN1341568A CN1341568A CN 01127854 CN01127854A CN1341568A CN 1341568 A CN1341568 A CN 1341568A CN 01127854 CN01127854 CN 01127854 CN 01127854 A CN01127854 A CN 01127854A CN 1341568 A CN1341568 A CN 1341568A
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Abstract
The present invention relates to a modified lignin sulfonate multifunctional water treatment agent for recirculated cooling water and its preparation method. It is characterized by that in the lignin sulfonate containing waste liquor produced by acid-pulpling for making paper, adding alkaline regulator, heating, adding oxidizing agent to make catalytic oxidation reaction, then adding radio initiator containing one or several metal ionic salts, sulfonating agent, molecular weight regulator and modifying agent to make sulfonation modification reaction so as to obtain the invented lignin sulfonate multifunctional water treatment agent. Said invention utilizes physical and chemical modification to change the contents of different functional groups of lignin sulfonate, introduces new functional group, changes its molecular weight distribution and modifies the lignin sulfonate into the invented water treatment agent with several functions of dispersing, inhibiting corrosion and resisting scale.
Description
Technical field
The byproduct Sulfite lignin that the present invention relates to pulping and paper-making are feedstock production recirculated cooling water treatment agent and preparation method thereof cheaply, and this water conditioner has multiple functions such as good dispersion, inhibition, scale inhibition.
Background technology
In whole process water, the consumption of water coolant accounts for 80% of total water amount greatly.In order to reach the purpose of saving Freshwater resources, protection environment, water coolant needs recycle, extensively adopts Water Treatment in Circulating Cooling System at present.Water coolant constantly recycles, and can produce mud, and causes the problems such as burn into fouling of equipment.For this reason, need handle recirculated cooling water.The processing of recirculated cooling water mainly contains methods such as chemicals treatment, magnetization processing, ozonize.Adding water conditioner at present is the most frequently used method.
The stages such as inorganic salt, polyelectrolyte, natural high moleculer eompound, acrylic copolymer and organic phosphonate have been experienced in the development of water conditioner, the industrial circulating cooling water water conditioner is occupied an leading position with chromium system, phosphorus system and acrylic acid series water conditioner in present existing technology, and progressively by simplification to the diversification technical development.The chromic salt corrosion mitigating effect is fine, but is limited owing to toxicity is also very big; Phosphorus line formulation has good anticorrosion-antiscaling effect, but easily produces the phosphoric acid salt crust and make body eutrophication cause public hazards such as " red tides " easily; The acrylate copolymer class has good scale inhibition effect to calcium carbonate scale, and its topmost shortcoming is that the calcium ion among the Yi Yushui reacts, and generates gelinite, makes water quality become muddy, thereby has limited its use.Also have the water-soluble polymers of other type in addition, as contain sulfonic group multipolymer, poly-maleinamic acid and polyamino acid.But each base polymer exists that toxicity is big, degraded is difficult, synthetic method is complicated and cost than problems such as height.
The common employing of the processing of industrial circulating cooling water adds the method for various water conditioners respectively, tends to like this cause that equipment increases, complex operation, expense increase, sometimes also can be short of money because of the phase transreactance of treatment agent, reduced the result of use of medicament.The appearance of multifunctional water treating agent can realize satisfying simultaneously by adding a kind of medicament the demand of several functions such as inhibition, scale inhibition, flocculation and sterilization.U.S. B.F.Goodrich chemical company has proposed a kind of multifunctional water treating agent in the EP220726 patent, it is to be formed by vinylformic acid and acrylamide copolymerization, has scale inhibition and dispersive function concurrently.At the beginning of the seventies, people such as Britain scholar Ballwin have developed a kind of polymeric silicon-containing aminomethyl or aminomethyl phosphonic acids and derivative thereof, and this class medicament can be used as inhibiter, Scale inhibitors and water purification agent.Present water conditioner mostly is the chemosynthesis product.Along with the shortage of world resource and the raising day by day of people's environmental consciousness, also more and more come into one's own with application for the research of Green Chemistry product in water treatment that with biomass is raw material.It is the multifunctional water treating agent CG-A series product that basic raw material is developed with natural polymer F691 that " Treatment of Industrial Water " 1994 discloses a kind of, and it has good flocculation, inhibition, scale inhibition or bactericidal property.Along with the increasingly stringent of environmental requirement, water conditioner is just towards multi-functional, nontoxic, easily degraded and the development of environment amenable green chemical.
Summary of the invention
The object of the present invention is to provide a kind of modified lignin sulfonate multifunctional water treatment agent, utilize the byproduct of pulping and paper-making---Sulfite lignin, by physics and chemical modification change the various functional groups of Sulfite lignin content, introduce new functional group, change its molecular weight distribution, the Sulfite lignin modification is become have dispersion, multi-functional water conditioners such as inhibition, scale inhibition.
The present invention also aims to provide a kind of preparation method of modified lignin sulfonate multifunctional water treatment agent.
The preparation method of modified lignin sulfonate multifunctional water treatment agent of the present invention may further comprise the steps:
(1) catalytic oxidation modification: contain in the acid polishing waste liquid of Sulfite lignin 1000 parts of weight, add 5～50 parts of weight alkaline conditioners, to the pH value be 8～10, be heated to 40～85 ℃, add 3～20 parts of strong oxidation class of weight oxygenants and carried out catalysis and oxidizing reaction 1～8 hour;
Described alkaline conditioner is metal hydroxides, NH
4OH is one or both and above mixture wherein;
Described strong oxidation class oxygenant is H
2O
2, KMnO
4, O
3, O
2Wherein a kind of;
(2) sulfonation and composite modified: add 5～20 parts of weight in the product of (1) and contain the redox initiator of one or more metal cation salt composition, the sulphonating agent of 5～200 parts of weight of adding, reacted 1-5 hour, add 2～10 parts of weight of molecular weight regulator and 3～50 parts of weight properties-correcting agent, reacted 1～3 hour, and obtained the Sulfite lignin multifunctional water treating agent after the cooling;
The redox initiator that described metal cation salt is formed is FeSO
4, FeCl
2, Fe
2(SO
4)
3, Cu (NO
3)
2, NaNO
3, KNO
3Wherein one or both and above mixture; Sulphonating agent is sodium bisulfite, S-WAT, Sodium Metabisulfite wherein one or both and above mixture; Molecular weight regulator is H
2SO
4, citric acid, formic acid, acetate wherein one or both and above mixture; Properties-correcting agent is organic amine, organic acid, silicone emulsion wherein one or both and above mixture.
The every gram product of the inventive method gained contains:
-SO
3H：0.7～3mmol.g
-1
-COOH：0.1～1mmol.g
-1
-OH：0.1～2mmol.g
-1
Following variation takes place in its structure of Sulfite lignin, physico-chemical property and the application performance of gained Sulfite lignin multifunctional water treating agent:
1, the variation of group and structure
Carboxyl is than original increase by 65% in the Sulfite lignin after the modification, and methoxyl group increases by 42%, and sulfonate radical is original 1.3 times, and molecular-weight average is original 1.2 times.
2, surperficial physical and chemical performance
Surface tension, the lathering property of Sulfite lignin multifunctional water treating agent and lignosulfonic acid sodium solution are seen Fig. 1 and table 1.The solution of sodium lignosulfonate can not form micelle-forming concentration, and micelle-forming concentration has then appearred in Sulfite lignin multifunctional water treating agent solution, and latherability is also little than sodium lignosulfonate.Adopt the alternating-current impedance method to measure the coverage of Sulfite lignin multifunctional water treating agent, see Fig. 2 in the metallic surface; Adopt spectrophotometric determination water conditioner to CaCO
3Dispersive ability is seen Fig. 3.Compare with sodium lignosulfonate, the Sulfite lignin multifunctional water treating agent is in the coverage of metallic surface with to CaCO
3Dispersive ability all be enhanced; As seen the surperficial physical and chemical performance of Sulfite lignin multifunctional water treating agent has greatly improved than unmodified sodium lignosulfonate.
Table 1
| Lathering property | Sodium lignosulfonate | The Sulfite lignin multifunctional water treating agent |
| Initial foam height, cm foam time, min | ????7.5 ????30 | ????1.6 ????＜1 |
3, inhibition, scale-inhibiting properties
Many merits water conditioner that the inventive method is made is compared with Sulfite lignin, has improved inhibition, scale-inhibiting properties significantly, compares with organic phosphine class corrosion inhibiting and descaling agent, and its inhibition resistance, dirty performance is better than or approaching with it, and measurement result is seen Fig. 3, table 2.The scale inhibition performance of Sulfite lignin multifunctional water treating agent reaches 80.1%, and dynamically corrosion inhibition rate reaches 97.3%.
Table 2
Experiment condition: 40 ℃ of pre-film temperatures, 2 days time, pre-film concentration 200mg/L, 14 days working times, 60 ℃ of temperature.Because the lignosulfonic acid molecules of salt contains functional groups such as phenolic hydroxyl group, alcoholic extract hydroxyl group, carboxyl, carbonyl, sulfonic group.Phenolic hydroxyl group, alcoholic extract hydroxyl group, carbonyl have sequestering action to high volence metal ion, are scale inhibition function groups.Sulfonic group and phenolic hydroxyl group can be adsorbed on the metal surface protection metal, and the phenolic ether structure has the effect of stable protective membrane, thereby have inhibition, rust inhibition.Sulfonated lignin are mixtures on the other hand, and molecular weight distribution is very wide, from several thousand to up to a million.High molecular partly can be used as flocculation agent, has the effect that purifies water, and low molecular weight part can be used as dispersion agent and Scale inhibitors.
| Inhibiter | Operation concentration (mg/L) | Dynamic corrosion inhibition rate % | Scale inhibition performance % | The water quality situation |
| Sodium lignosulfonate | ????50 | ????48.1 | ????15.5 | Muddiness is turned to be yellow and many foam turbidity: 87.6mg/ is arranged |
| The Sulfite lignin multifunctional water treating agent | ????25 | ????95.5 | ????75.1 | The pureer and impureer degree of water quality: 10.2mg/L |
| ????50 | ????97.3 | ????80.1 | ||
| Organic phosphine class water conditioner | ????25 | ????78.0 | ????76.2 | Muddy, jaundice turbidity: 56.8mg/L |
| ????50 | ????86.5 | ????78.5 |
Sulfite lignin multifunctional water treating agent raw material sources are abundant, and cheap, production cost only is about 50% of organic phosphine class water conditioner, and production technique is comparatively simple, is a kind of water conditioner that development potentiality is arranged very much.
Fig. 1 is the concentration of modified lignin sulfonate multifunctional water treatment agent of the present invention and the relation of solution surface tension;
Fig. 2 be the concentration of the described water conditioner of Fig. 1 with in the relation of metallic surface coverage;
Fig. 3 is that the concentration of the described water conditioner of Fig. 1 is to CaCO
3The dispersive ability of dirt;
Fig. 4 is the concentration of the described water conditioner of Fig. 1 and the relation of static-state scale inhibition rate.
The specific embodiment
(1) catalytic oxidation modification: selecting concentration is the acid polishing waste liquid solution that contains lignosulphonates 2500 gram (solid content is 1000 grams) of 40% weight, adds 10 gram NaOH, to pH value be 8, be heated to 80 ℃, the 30% weight H of dropping 30ml2O
2H
2O
2Carried out catalysis and oxidation reaction 2 hours;
(2) sulfonation and composite modified: add 2 gram FeCl in the product of (1)3Fe with 6 grams2(SO
4)
3The sodium hydrogensulfites of the redox initiator that forms, adding 50 grams reacted 1 hour, added 20% (weight) dilute sulfuric acid and the 10 gram n-butylamines of 10ml, reacted 2 hours, obtained the lignosulphonates multifunctional water treating agent after the cooling.
Embodiment 2
(1) catalytic oxidation modification: selecting concentration is the acid polishing waste liquid solution that contains lignosulphonates 2500 grams (solid content is 1000 grams) of 40% weight, adds the NH of 20 grams4OH, to the pH value be 8, be heated to 80 ℃, drip the 30% weight H of 30ml2O
2Carried out catalysis and oxidation reaction 2 hours;
(2) sulfonation and composite modified: the FeCl that adds 3 grams in the product of (1)3Cu (NO with 2 grams3)
2The sodium sulfites of the redox initiator that forms, adding 100 grams reacted 1.5 hours, added 10 gram citric acid and 10ml silicone emulsions, reacted 2 hours, obtained the lignosulphonates multifunctional water treating agent after the cooling.
(1) catalytic oxidation modification: selecting concentration is the acid polishing waste liquid solution that contains lignosulphonates 2500 gram (solid content is 1000 grams) of 40% weight, adds 15 gram KOH, to pH value be 9, be heated to 80 ℃, add 8 and restrain KMnO4Carried out catalysis and oxidation reaction 2 hours;
(2) sulfonation and composite modified: add 3 gram NaNO in the product of (1)3FeSO with 4 grams4The Sodium Metabisulfites of the redox initiator that forms, adding 25 grams reacted 2 hours, added 12 gram citric acid and 20ml n-butyric acies, reacted 2 hours, obtained the lignosulphonates multifunctional water treating agent after the cooling.
Embodiment 4
(1) catalytic oxidation modification: selecting concentration is the acid polishing waste liquid solution that contains lignosulphonates 2500 grams (solid content is 1000 grams) of 40% weight, adds the Ca (OH) of 10 grams2, to the pH value be 9, be heated to 80 ℃, add 10 gram KMnO4Carried out catalysis and oxidation reaction 2 hours;
(2) sulfonation and composite modified: add 2 gram NaNO in the product of (1)3With 5 gram Cu (NO3)
2The Sodium Metabisulfites of the redox initiator that forms, adding 30 grams reacted 2 hours, added 10 gram acetic acid and 30 gram laurate, reacted 2 hours, obtained the lignosulphonates multifunctional water treating agent after the cooling.
Claims (2)
1, the preparation method of modified lignin sulfonate multifunctional water treatment agent is characterized in that may further comprise the steps:
(1) catalytic oxidation modification: contain in the acid polishing waste liquid of Sulfite lignin 1000 parts of weight, add 5～50 parts of weight alkaline conditioners, to the pH value be 8～10, be heated to 40～85 ℃, add 3～20 parts of strong oxidation class of weight oxygenants and carried out catalysis and oxidizing reaction 1～8 hour; Described alkaline conditioner is metal hydroxides, NH
4OH is one or both and above mixture wherein; Described strong oxidation class oxygenant is H
2O
2, KMnO
4, O
3, O
2Wherein a kind of;
(2) sulfonation and composite modified: add 5～20 parts of weight in the product of (1) and contain the redox initiator of one or more metal cation salt composition, the sulphonating agent of 5～200 parts of weight of adding, reacted 1-5 hour, add 2～10 parts of weight of molecular weight regulator and 3～50 parts of weight properties-correcting agent, reacted 1～3 hour, and obtained the Sulfite lignin multifunctional water treating agent after the cooling; The redox initiator that described metal cation salt is formed is FeSO
4, FeCl
2, Fe
2(SO
4)
3, Cu (NO
3)
2, NaNO
3, KNO
3Wherein one or both and above mixture; Sulphonating agent is sodium bisulfite, S-WAT, Sodium Metabisulfite wherein one or both and above mixture; Molecular weight regulator is H
2SO
4, citric acid, formic acid, acetate wherein one or both and above mixture; Properties-correcting agent is organic amine, organic acid, silicone emulsion wherein one or both and above mixture.
2, the modified lignin sulfonate multifunctional water treatment agent of the described method preparation of claim 1.
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|---|---|---|---|
| CN 01127854 CN1202027C (en) | 2001-09-14 | 2001-09-14 | Modified lignin sulfonate multifunctional water treatment agent and its preparation method |
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|---|---|---|---|
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| CN1202027C CN1202027C (en) | 2005-05-18 |
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|---|---|---|---|
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103408148A (en) * | 2013-07-30 | 2013-11-27 | 杭州天城环境发展有限公司 | Anti-fouling complex alkali solution for Fenton reaction |
| CN104659369A (en) * | 2015-03-26 | 2015-05-27 | 天能集团江苏科技有限公司 | Preparation method of modified sodium lignosulfonate for lead-acid battery |
| CN107010866A (en) * | 2017-03-31 | 2017-08-04 | 鹤山市超牌碳酸钙有限公司 | A kind of height lignosulfonate sulfonate water reducer and preparation method thereof |
| CN107746118A (en) * | 2017-09-26 | 2018-03-02 | 浙江海洋大学 | A kind of water treatment agent and preparation method thereof |
| CN108439618A (en) * | 2018-03-14 | 2018-08-24 | 兖矿水煤浆气化及煤化工国家工程研究中心有限公司 | A kind of coal gasification buck scale preventative and preparation method thereof |
| CN109231507A (en) * | 2018-10-08 | 2019-01-18 | 曹布道 | A kind of sewage-treating agent and preparation method thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101624517B (en) * | 2009-07-29 | 2011-03-23 | 牡丹江市红林化工有限责任公司 | Ferrimanganic lignosulfonate diluent agent for drilling fluid and preparation process thereof |
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2001
- 2001-09-14 CN CN 01127854 patent/CN1202027C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103408148A (en) * | 2013-07-30 | 2013-11-27 | 杭州天城环境发展有限公司 | Anti-fouling complex alkali solution for Fenton reaction |
| CN104659369A (en) * | 2015-03-26 | 2015-05-27 | 天能集团江苏科技有限公司 | Preparation method of modified sodium lignosulfonate for lead-acid battery |
| CN104659369B (en) * | 2015-03-26 | 2017-01-18 | 天能集团江苏科技有限公司 | Preparation method of modified sodium lignosulfonate for lead-acid battery |
| CN107010866A (en) * | 2017-03-31 | 2017-08-04 | 鹤山市超牌碳酸钙有限公司 | A kind of height lignosulfonate sulfonate water reducer and preparation method thereof |
| CN107746118A (en) * | 2017-09-26 | 2018-03-02 | 浙江海洋大学 | A kind of water treatment agent and preparation method thereof |
| CN107746118B (en) * | 2017-09-26 | 2020-08-04 | 浙江海洋大学 | Water treatment agent and preparation method thereof |
| CN108439618A (en) * | 2018-03-14 | 2018-08-24 | 兖矿水煤浆气化及煤化工国家工程研究中心有限公司 | A kind of coal gasification buck scale preventative and preparation method thereof |
| CN109231507A (en) * | 2018-10-08 | 2019-01-18 | 曹布道 | A kind of sewage-treating agent and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN1202027C (en) | 2005-05-18 |
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Granted publication date: 20050518 Termination date: 20120914 |