CN110483807A - A kind of method that soda spent liquor prepares ligno-sulfate based plasticizer - Google Patents
A kind of method that soda spent liquor prepares ligno-sulfate based plasticizer Download PDFInfo
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- CN110483807A CN110483807A CN201910834026.9A CN201910834026A CN110483807A CN 110483807 A CN110483807 A CN 110483807A CN 201910834026 A CN201910834026 A CN 201910834026A CN 110483807 A CN110483807 A CN 110483807A
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- lignin
- spent liquor
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- solid content
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/16—Sulfur-containing compounds
- C04B24/18—Lignin sulfonic acid or derivatives thereof, e.g. sulfite lye
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/302—Water reducers
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Structural Engineering (AREA)
- Biochemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Paper (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a kind of methods that soda spent liquor prepares ligno-sulfate based plasticizer, comprising steps of soda spent liquor is concentrated using pre-filtering, ultrafiltration membrane first, cellulose, lignin and lye are separated, the lignin concentrate after concentration prepares lignosulfonates by oxidation, sulfonation.The method that soda spent liquor of the invention prepares ligno-sulfate based plasticizer, it is effectively utilized papermaking wastewater, both reduced papermaking wastewater discharge to environment pollution while or to the higher value application realized to waste, there is no the pulp mill of alkali collection especially considerable itself small scale；Have sulfonation degree high using lignosulfonates produced by the invention simultaneously, pulp flowage is high, the good application characteristic of water-reducing effect.
Description
Technical field
The present invention relates to pulp technology for making paper more particularly to a kind of soda spent liquor to prepare lignosulfonates diminishing
The method of agent.
Background technique
Pulping and paper-making industry is one of the industry of China's heavy contamination, wherein most important pollution source is pulping waste liquor
Pollution, and wherein lignin is the main component of waste liquid.Because lignin is larger by steaming preparation destruction in pulping process, add
Upper different material also causes the increasing that lignin utilizes difficulty to a certain extent, and pulping waste liquor producing level is very low at present,
Only be used as fuel combustion recover energy and waste liquid in alkali.
Lignin be by aromatic alcohol polymerization and the substance constituted, be present in lignum, main function is logical
It crosses formation intertexture net and carrys out sclereid wall, be the main ingredient of secondary wall.Lignin is predominantly located between cellulose fibre, plays branch
Support, resistance to compression effect.In xylophyta, lignin accounts for about 20% to 25%, is that the natural polymer abundant of nature second is (fine
The first) tieing up element is.Lignin is nontoxic, has fabulous versatility in aspect of performance, is industrially widely used.In addition, wooden
It containing there are many group in quality structure, is easy to happen and chemically reacts and be modified, can be used for producing a variety of chemical materials, such as disperse
Agent, cement water reducing agent etc..Lignin can substitute some nondegradable materials as a kind of degradable environment friendly material well,
Have very important significance to environmental protection tool.
Soda pulping is one of pulping process of mainstream, and the waste liquid that digestion process generates contains a large amount of lignin, and
Pulping and paper-making industry only realizes that seldom a part of waste liquid is used at present, wherein a large amount of soda spent liquor still without
To being recovered energy and boiling lye using being also only used for burning.Thus, it would be highly desirable to research and develop a kind of utilization of soda spent liquor
Approach realizes the efficient utilization to soda spent liquor, realizes the higher value application to resource.
Summary of the invention
The present invention is to improve soda spent liquor resource utilization rate, solves current soda spent liquor treatment process
There are the problem of, a kind of method that soda spent liquor prepares ligno-sulfate based plasticizer is provided.
The method that soda spent liquor provided by the invention prepares ligno-sulfate based plasticizer, is particularly suitable for the scale of construction
High-valued its pulp-making waste-water of processing in the small-sized pulp mill of small no alkali collection；Its preparation method obtains while reducing environmental pollution
Obtain the ligno-sulfate based plasticizer that high-valued sulfonation degree is high, pulp flowage is high, water-reducing effect is good.
To achieve the above object, it adopts the following technical scheme that
The first aspect of the invention provides a kind of method that soda spent liquor prepares ligno-sulfate based plasticizer,
The following steps are included:
(1) using the fiber-like impurity in prefilter removal soda spent liquor, waste liquid is obtained；
(2) by waste liquid cross ultrafiltration membrane carry out concentration, control treated concentration fluid solid content in 15-30%, density
1.08-1.20g/mL obtains lignin concentrate, and content of lignin is up to 50-80% in solid content；
(3) hydrogen peroxide is added into lignin concentration and carries out oxidation reaction, control pH is reacted in 8-13 in 50-75 DEG C
30-100min；
(4) formaldehyde is added into the lignin concentration after oxidation and carries out polycondensation reaction, in 50-75 DEG C of reaction 30-100min,
To increase the molecular weight of lignin, lignin condensation polymer is obtained；
(5) sulfonating agent progress sulfonating reaction is added into lignin condensation polymer to obtain in 80-100 DEG C of reaction 60-150min
Lignosulfonates；
(6) lignosulfonates after sulfonating reaction are spray-dried to get ligno-sulfate based plasticizer.
Further, the solid content of soda spent liquor described in step (1) is 8-15%, density 1.03-
1.08g/mL, pH value 10.5-13.5.
Further, the aperture of prefilter described in step (1) is 1-20 μm, and filtered fiber-like impurity is back to
Papermaking workshop section.
Further, the molecular weight of ultrafiltration membrane described in step (2) be 1000-10000,40-70 DEG C for the treatment of conditions, into film
Pressure 10-50bar；Filtered filtrate is back to slurrying workshop section containing alkali.
Further, concentration of hydrogen peroxide described in step (3) is 30wt%, and dosage is in the concentrate solid content
The 10-30wt% of content of lignin.
Further, concentration of formaldehyde described in step (4) is 37wt%, and dosage is wooden in the concentrate solid content
The 10-50wt% of cellulose content.
Further, sulfonating agent described in step (5) is sulfur dioxide, sodium sulfite or sodium hydrogensulfite.
Further, the dosage of sulfonating agent described in step (5) is the 10- of content of lignin in the concentrate solid content
50wt%.
Further, spray drying described in step (6) uses atomizer drier pair, inlet steam temperature 200-
240 DEG C, 90-120 DEG C of outlet temperature.
The second aspect of the invention is to provide a kind of the wooden of the soda spent liquor preparation of method as described above
Plain sulfonate water reducer.
The present invention by adopting the above technical scheme, compared with prior art, has the following technical effect that
The method that soda spent liquor provided by the invention prepares ligno-sulfate based plasticizer, the fibre of pre-filtering recycling
Dimension substance is back to papermaking workshop section, and ultrafiltration retains lignin and is used for sulfonation, is back to slurrying workshop section through lye；The processing work
Discharge of wastewater is greatly reduced in skill, simplifies the processing step of Sulphonation of Lignin, can effectively shorten the production cycle, has efficient
Property；The lignosulfonates of production have sulfonation degree high simultaneously, and pulp flowage is high, the good application characteristic of water-reducing effect.
Specific embodiment
The present invention is described in more detail below by specific embodiment, for a better understanding of the present invention,
But following embodiments are not intended to limit the scope of the invention.
Embodiment 1
A kind of method that soda spent liquor prepares ligno-sulfate based plasticizer, comprising the following steps:
(1) using soda spent liquor as raw material, solid content exists in 8-15%, density 1.03-1.08g/mL, pH value
10.5-13.5 content of organics 60-70%；Inorganic content is 30-40%；Lignin accounts for the 25- of black liquor solid
35%；
(2) 5um prefilter is used to be filtered processing to solid content for 10% black liquor；
(3) treatment fluid is concentrated by ultrafiltration using 3000 molecular weight ultrafiltration membranes, material is alkaline-resisting PS membrane, treatment temperature
45 DEG C, feed pressure 20bar, it is 18% that concentration fluid solid content is obtained after processing, and lignin is the 60% of solid content；
(4) 12% hydrogen peroxide is added, 50 DEG C of reaction temperature, reaction time 60min, reacts pH 9；
(5) formaldehyde of addition 15%, 55 DEG C of reaction temperature, reaction time 60min；
(6) sulfur dioxide of addition 15%, 85 DEG C of reaction temperature, reaction time 60min；
(7) sulfonated liquid is spray-dried using atomizer drier, 200 DEG C of inlet temperature, outlet temperature 90
DEG C, obtain the thinner lignin sulfonic acid salt powder of particle, solid content 93%.
Embodiment 2
A kind of method that soda spent liquor prepares ligno-sulfate based plasticizer, comprising the following steps:
(1) using soda spent liquor as raw material, solid content exists in 8-15%, density 1.03-1.08g/mL, pH value
10.5-13.5 content of organics 60-70%；Inorganic content is 30-40%；Lignin accounts for the 25- of black liquor solid
35%；
(2) 10um prefilter is used to be filtered processing to solid content for 12% black liquor；
(3) treatment fluid is concentrated by ultrafiltration using 5000 molecular weight ultrafiltration membranes, material is alkaline-resisting PS membrane, treatment temperature
55 DEG C, feed pressure 30bar, it is 22% that concentration fluid solid content is obtained after processing, and lignin is the 65% of solid content；
(4) 19% hydrogen peroxide is added, 65 DEG C of reaction temperature, reaction time 80min, reacts pH 9；
(5) formaldehyde of addition 15%, 65 DEG C of reaction temperature, reaction time 70min；
(6) sulfur dioxide of addition 15%, 90 DEG C of reaction temperature, reaction time 90min；
(7) sulfonated liquid is spray-dried using atomizer drier, 220 DEG C of inlet temperature, outlet temperature 100
DEG C, obtain the thinner lignin sulfonic acid salt powder of particle, solid content 95%.
Embodiment 3
A kind of method that soda spent liquor prepares ligno-sulfate based plasticizer, comprising the following steps:
(1) using soda spent liquor as raw material, solid content exists in 8-15%, density 1.03-1.08g/mL, pH value
10.5-13.5 content of organics 60-70%；Inorganic content is 30-40%；Lignin accounts for the 25- of black liquor solid
35%；
(2) 16um prefilter is used to be filtered processing to solid content for 14% black liquor；
(3) treatment fluid is concentrated by ultrafiltration using 8500 molecular weight ultrafiltration membranes, material is alkaline-resisting PS membrane, treatment temperature
65 DEG C, feed pressure 45bar, it is 27% that concentration fluid solid content is obtained after processing, and lignin is the 70% of solid content；
(4) 26% hydrogen peroxide is added, 70 DEG C of reaction temperature, reaction time 80min, reacts pH 9；
(5) formaldehyde of addition 15%, 70 DEG C of reaction temperature, reaction time 90min；
(6) sulfur dioxide of addition 15%, 95 DEG C of reaction temperature, reaction time 120min；
(7) sulfonated liquid is spray-dried using atomizer drier, 240 DEG C of inlet temperature, outlet temperature 110
DEG C, obtain the thinner lignin sulfonic acid salt powder of particle, solid content 97%.
Performance detection
Water-reducing agent prepared by embodiment 1-3, using standard cement, volume presses the 0.15% of cement quality, according to GB
8076-2008 " concrete admixture ", surveys its water-reducing rate, the slump and slump-loss.Concrete proportioning are as follows: cement 350kg/
m3, sand 800kg/m3, flyash 1050kg/m3, in 210 ± 10mm, data are shown in Table 1 for slump control.
Table 1
| Water-reducing rate % | Slump mm | Divergence mm | |
| Benchmark | — | 210/580 | 145/380 |
| Embodiment 1 | 35 | 225/570 | 185/475 |
| Embodiment 2 | 51 | 235/590 | 235/515 |
| Embodiment 3 | 46 | 230/580 | 215/505 |
The embodiment 1-3 water-reducing agent prepared and ordinary water-reducing agent are subjected to air content, the detection of bleeding rate, selection cement is
Portland cement, rolling over solid volume is the 0.1% of cement, and data are shown in Table 2.
Table 2
| Air content % | Bleeding rate % | |
| Ordinary water-reducing agent | 45 | 4.5 |
| Embodiment 1 | 28 | 2.3 |
| Embodiment 2 | 16 | 1.0 |
| Embodiment 3 | 22 | 1.5 |
Specific embodiments of the present invention are described in detail above, but it is merely an example, the present invention is simultaneously unlimited
It is formed on particular embodiments described above.To those skilled in the art, any couple of present invention carries out equivalent modifications and
Substitution is also all among scope of the invention.Therefore, without departing from the spirit and scope of the invention made by equal transformation and
Modification, all should be contained within the scope of the invention.
Claims (10)
1. a kind of method that soda spent liquor prepares ligno-sulfate based plasticizer, which comprises the following steps:
(1) using the fiber-like impurity in prefilter removal soda spent liquor, waste liquid is obtained；
(2) by waste liquid cross ultrafiltration membrane carry out concentration, control treated concentration fluid solid content in 15-30%, density 1.08-
1.20g/mL obtains lignin concentrate, and content of lignin is up to 50-80% in solid content；
(3) hydrogen peroxide is added into lignin concentration and carries out oxidation reaction, control pH in 8-13, in 50-75 DEG C of reaction 30-
100min；
(4) formaldehyde progress polycondensation reaction is added into the lignin concentration after oxidation to obtain wooden in 50-75 DEG C of reaction 30-100min
Quality condensation polymer；
(5) sulfonating agent progress sulfonating reaction is added into lignin condensation polymer to obtain wooden in 80-100 DEG C of reaction 60-150min
Plain sulfonate；
(6) lignosulfonates after sulfonating reaction are spray-dried to get ligno-sulfate based plasticizer.
2. preparation method according to claim 1, which is characterized in that soda spent liquor described in step (1)
Solid content is 8-15%, density 1.03-1.08g/mL, pH value 10.5-13.5.
3. preparation method according to claim 1, which is characterized in that the aperture of prefilter described in step (1) is
1-20 μm, filtered fiber-like impurity is back to papermaking workshop section.
4. preparation method according to claim 1, which is characterized in that the molecular weight of ultrafiltration membrane described in step (2) is
1000-10000,40-70 DEG C for the treatment of conditions, into film pressure 10-50bar；Filtered filtrate is back to slurrying workshop section containing alkali.
5. preparation method according to claim 1, which is characterized in that concentration of hydrogen peroxide described in step (3) is
30wt%, dosage are the 10-30wt% of content of lignin in the concentrate solid content.
6. preparation method according to claim 1, which is characterized in that concentration of formaldehyde described in step (4) is 37wt%,
Its dosage is the 10-50wt% of content of lignin in the concentrate solid content.
7. preparation method according to claim 1, which is characterized in that sulfonating agent described in step (5) be sulfur dioxide,
Sodium sulfite or sodium hydrogensulfite.
8. preparation method according to claim 1, which is characterized in that the dosage of sulfonating agent described in step (5) is institute
State the 10-50wt% of content of lignin in concentrate solid content.
9. preparation method according to claim 1, which is characterized in that spray drying is using centrifugation described in step (6)
Formula spray dryer pair, 200-240 DEG C of inlet steam temperature, 90-120 DEG C of outlet temperature.
10. a kind of lignosulfonates such as the soda spent liquor preparation of any one of claims 1-9 the method subtract
Aqua.
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Cited By (4)
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| CN111848976A (en) * | 2020-07-02 | 2020-10-30 | 上海昶法新材料有限公司 | Method for preparing lignosulfonate by using dissolving pulp precooking waste liquid and application |
| CN112961373A (en) * | 2021-02-19 | 2021-06-15 | 上海昶法新材料有限公司 | Method for preparing high-temperature-resistant lignin asphalt emulsifier through microwave catalysis |
| CN114000369A (en) * | 2021-09-28 | 2022-02-01 | 山东格瑞兰德添加剂有限公司 | Method for preparing anionic surfactant from ultrafiltration sulfate pulping black liquor |
| CN115926191A (en) * | 2022-12-27 | 2023-04-07 | 上海昶法新材料有限公司 | Method for preparing lignin asphalt emulsifier by using sulfate pulping waste liquid |
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| CN114000369A (en) * | 2021-09-28 | 2022-02-01 | 山东格瑞兰德添加剂有限公司 | Method for preparing anionic surfactant from ultrafiltration sulfate pulping black liquor |
| CN115926191A (en) * | 2022-12-27 | 2023-04-07 | 上海昶法新材料有限公司 | Method for preparing lignin asphalt emulsifier by using sulfate pulping waste liquid |
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Application publication date: 20191122 |