CN103666606B - A kind of Lignins slurries additive agent and preparation method thereof - Google Patents
A kind of Lignins slurries additive agent and preparation method thereof Download PDFInfo
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- CN103666606B CN103666606B CN201310583078.6A CN201310583078A CN103666606B CN 103666606 B CN103666606 B CN 103666606B CN 201310583078 A CN201310583078 A CN 201310583078A CN 103666606 B CN103666606 B CN 103666606B
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 81
- 229920005610 lignin Polymers 0.000 title claims abstract description 81
- 239000002002 slurry Substances 0.000 title claims abstract description 69
- 230000000996 additive effect Effects 0.000 title claims abstract description 54
- 239000000654 additive Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 150000001299 aldehydes Chemical class 0.000 claims abstract description 50
- 239000003513 alkali Substances 0.000 claims abstract description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 44
- 150000002576 ketones Chemical class 0.000 claims abstract description 32
- 239000007864 aqueous solution Substances 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 239000002994 raw material Substances 0.000 claims abstract description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 77
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 56
- 239000000203 mixture Substances 0.000 claims description 37
- 150000001875 compounds Chemical class 0.000 claims description 36
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 claims description 30
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 27
- 239000013067 intermediate product Substances 0.000 claims description 22
- 239000008098 formaldehyde solution Substances 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 20
- 230000007062 hydrolysis Effects 0.000 claims description 18
- 238000006460 hydrolysis reaction Methods 0.000 claims description 18
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 12
- 239000012263 liquid product Substances 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 235000001018 Hibiscus sabdariffa Nutrition 0.000 claims description 10
- 235000005291 Rumex acetosa Nutrition 0.000 claims description 10
- 240000007001 Rumex acetosella Species 0.000 claims description 10
- 235000003513 sheep sorrel Nutrition 0.000 claims description 10
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 claims description 9
- 235000010262 sodium metabisulphite Nutrition 0.000 claims description 9
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 8
- 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 claims description 6
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 6
- CCGKOQOJPYTBIH-UHFFFAOYSA-N ethenone Chemical compound C=C=O CCGKOQOJPYTBIH-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- TZMFJUDUGYTVRY-UHFFFAOYSA-N pentane-2,3-dione Chemical compound CCC(=O)C(C)=O TZMFJUDUGYTVRY-UHFFFAOYSA-N 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- PODWXQQNRWNDGD-UHFFFAOYSA-L sodium thiosulfate pentahydrate Chemical compound O.O.O.O.O.[Na+].[Na+].[O-]S([S-])(=O)=O PODWXQQNRWNDGD-UHFFFAOYSA-L 0.000 claims description 6
- 239000003245 coal Substances 0.000 abstract description 36
- 238000006277 sulfonation reaction Methods 0.000 abstract description 23
- 230000000694 effects Effects 0.000 abstract description 12
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 238000009736 wetting Methods 0.000 abstract description 6
- 230000002153 concerted effect Effects 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 19
- 238000012545 processing Methods 0.000 description 7
- 238000004537 pulping Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000007031 hydroxymethylation reaction Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 108010029541 Laccase Proteins 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 229920005552 sodium lignosulfonate Polymers 0.000 description 3
- 229920001732 Lignosulfonate Polymers 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000003250 coal slurry Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 235000019357 lignosulphonate Nutrition 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- -1 phenyl aldehyde Chemical class 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002789 polymer coal Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 150000003385 sodium Chemical class 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 244000082204 Phyllostachys viridis Species 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- 241000209140 Triticum Species 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- 239000002802 bituminous coal Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- YDEXUEFDPVHGHE-GGMCWBHBSA-L disodium;(2r)-3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Na+].[Na+].COC1=CC=CC(C[C@H](CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O YDEXUEFDPVHGHE-GGMCWBHBSA-L 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Landscapes
- Phenolic Resins Or Amino Resins (AREA)
Abstract
The present invention relates to a kind of Lignins slurries additive agent and preparation method thereof, belong to coal water slurry production technical field.Comprise the following raw material according to weight parts: alkali lignin aqueous solution 200-300 part, sulphonating agent I 10-20 part, sulphonating agent II 50-90 part, ketone thing 50-140 part, aldehydes 100-200 part, water 500-600 part; Lignins slurries additive agent of the present invention improves wetting ability and sulfonation degree, adopts coal water slurry good fluidity prepared by this additive, and adopts the concerted reaction of multiple sulphonating agent in the formula of additive of the present invention, highlight sulfonation effect.
Description
Technical field
The present invention relates to a kind of slurries additive agent and preparation method thereof, more particularly, the present invention relates to a kind of Lignins slurries additive agent and preparation method thereof, belong to coal water slurry production technical field.
Background technology
Alkali lignin is the by product of paper industry, and modified alkali lignin can use as slurries additive agent, effectively strengthens utilization of resources.
Sulfonation reaction is modified as to alkali lignin the best.Because the reaction activity of alkali lignin is higher, activity is lower, and usual Direct Sulfonation reaction is all carry out just reaching higher sulfonation degree under the conditions such as High Temperature High Pressure or other auxiliary such as microwave radiations.Industrial alkali lignin sodium sulfonate just under high-temperature pressure (120-200 DEG C) carry out alkali lignin sulfonation, but which facility investment in early stage is comparatively large, has press operation also more complicated.
Patent CN101235055 " a kind of method manufacturing sodium lignosulfonate " preparing product needs to react at 125-145 DEG C.
Patent CN101475604 " a kind of method preparing highly sulfonated sodium lignosulfonate " describes the synthesis of the auxiliary lower highly sulfonated sodium lignosulfonate in microwave radiation, but this mode present stage is difficult to realize industrialization promotion.And the quality product obtained for the sulfonation under normal pressure is at present uneven.
Patent CN102199268 " laccase activation modification sulfonated wheat-strew lignin amphiphilic polymer and preparation method thereof and application " describes the preparation method of laccase activation modification sulfonated wheat-strew lignin amphiphilic polymer, but processing condition are wayward, laccase is expensive, and the time of activation xylogen is longer.
Patent CN1434068 " method of producing sulfonated lignin " describes producing sulfonated lignin, and first add formaldehyde, after then adding sulphite reacting by heating, drying obtains product.But the modified lignin resin system additive obtained with upper type often wetting ability does not reach requirement, and sulfonation degree is also on the low side.This is because xylogen is too many as bleed slurries additive agent, and in causing coal water slurry to stir, bubble is too many, and mobility is not good.Some is too many to the acidic ph modifier used during lignin modification, causes sodium sulphate content in product many, easy crystallization in winter.
It is CN102585940A that State Intellectual Property Office discloses a publication number in 2012.7.18, name is called the patent of invention of " Sulfomethylated alkali lignin-formaldehyde-sulfonated acetone polymer coal water slurry additive ", which disclose a kind of Sulfomethylated alkali lignin-formaldehyde-sulfonated acetone polymer coal water slurry additive and preparation method thereof, the mass fraction of feed composition and each component is: alkali lignin 11.5-20.0 part, sulphonating agent 4.9-10.0 part, alkaline conditioner 0.1-0.8 part, acetone 4.5-10.0 part, formaldehyde 5.4-13.5 part, water 47.3-67.2 part.Its step of preparation process is as follows: alkali lignin and a certain amount of formaldehyde and sulphonating agent are reacted, prepare sulfomethylation alkali lignin; Again by alkaline conditioner and sulphonating agent and acetone generation catalysis sulfonation reaction, obtain sulfonated acetone prepolymer, add the sulfomethylation alkali lignin and the further polymerization reaction take place of formaldehyde solution that have prepared again, form the slurries additive agent containing sulfonic group, hydroxyl and alkyl active group, improve product dispersiveness and stability.Method of the present invention is simple, and starting material are easy to get, with short production cycle, and product stability is good, nontoxic, and uses not by season, and region limits, and is convenient to deposit and transport, achieves the higher value application of xylogen.
It is large to there is acetone consumption in the additive in above-mentioned patent, and employs alkaline conditioner, causes cost to increase and slurries additive agent wetting ability is low, sulfonation degree is low, causes the problem that coal water slurry mobility is not good; In addition, sulfomethylation alkali lignin is mixed with sulfonated acetone thing add formaldehyde solution again in preparation method in above-mentioned patent, temperature controls not good rear easy production precipitation, and formaldehyde is easy and in sulfomethylation, residual formaldehyde (as phenyl aldehyde) reacts, cause wastage of material, total reaction time is long simultaneously, and efficiency is low.
Summary of the invention
The present invention is intended to solve that Lignins slurries additive agent wetting ability of the prior art is low, sulfonation degree is low, cause the problem that coal water slurry mobility is not good, a kind of Lignins slurries additive agent is provided, improves wetting ability and sulfonation degree, and coal water slurry mobility can not be caused not good.
In order to achieve the above object, the technical solution used in the present invention is as follows:
A kind of Lignins slurries additive agent, is characterized in that: comprise the following raw material according to weight parts:
Alkali lignin aqueous solution 200-300 part
Sulphonating agent I 10-20 part
Sulphonating agent II 50-90 part
Ketone thing 50-140 part
Aldehydes 100-200 part
Water 150-250 part;
Described sulphonating agent I and sulphonating agent II is one or more the mixture in S-WAT, sodium bisulfite, Sodium Pyrosulfite, Sulfothiorine, thionamic acid, thionamic acid sodium; Described ketone thing is one or more the mixture in acetone, ketene, methyl phenyl ketone, methyl ethyl diketone, pimelinketone; Described aldehydes is the mixture of one or both arbitrary proportions of formalin, acetaldehyde solution.
Above-mentioned sulphonating agent I can be identical with sulphonating agent II, also can be different.
Sulphonating agent I of the present invention and sulphonating agent II be multiple mixture or wherein a kind of sulphonating agent is multiple mixture time, if containing S-WAT, so the mol ratio of S-WAT and other compound summations is >=1:1, and the mol ratio between other compounds is arbitrary proportion; If not containing S-WAT, the mol ratio so between other compounds is arbitrary proportion.
When ketone thing of the present invention is multiple mixture, if containing acetone, so the mol ratio of acetone and other compound summations is >=3:2, and the mol ratio between other compounds is arbitrary proportion; If not containing acetone, the mol ratio so between other compounds is arbitrary proportion.
Ketone thing of the present invention is acetone.
The concentration of formaldehyde solution of the present invention is the aqueous solution of 30-40%, the aqueous solution of acetaldehyde solution to be concentration be 35-40%.
Aldehydes of the present invention is formaldehyde solution.
In the present invention, described alkali lignin is black liquid product, is not limited to wheat straw alkali lignin, bamboo wood alkali lignin etc.
A preparation method for Lignins slurries additive agent, is characterized in that: comprise following processing step:
A, preparation quality mark are the alkali lignin aqueous solution of 25-45%;
B, get sulphonating agent I and part aldehydes, stir, add the alkali lignin aqueous solution, react 2-3h at temperature is 80-90 DEG C after, obtain intermediate product A, stand-by.
C, to get sulphonating agent II soluble in water, after hydrolysis for some time, adds ketone thing, at temperature is 45-55 DEG C, reacts 0.5-1.5h; Drip remaining aldehydes wherein again, after dropwising, add stand-by intermediate product A wherein, after mixing at 75-85 DEG C isothermal reaction 1-2h, obtain sorrel liquid product and Lignins slurries additive agent of the present invention.
The present invention is in step B and step C, and the mass ratio of the aldehydes in described step B and the aldehydes in step C is 1:2.5-4.5.
The present invention is in step C, and described hydrolysis for some time refers to hydrolysis 10-45 minute.
The present invention is in step C, and the remaining aldehydes of described dropping refers to and to drip off in 0.5-1h.
The present invention compared with prior art has following outstanding advantages:
1, Lignins slurries additive agent of the present invention improves wetting ability and sulfonation degree, adopt coal water slurry good fluidity prepared by this additive, and adopt the concerted reaction of multiple sulphonating agent in the formula of additive of the present invention, highlight sulfonation effect, material rate is different very large on the impact of price in addition, the total mass ratio of aldehydes of the present invention and ketone thing is about 2:1, and does not need to add alkaline conditioner, makes cost of the present invention lower.It is comparatively wide that additive of the present invention is suitable for coal scope, and better to bituminous coal effect, addition is the 0.2-0.6% of coal butt amount.
2, synthesis technique of the present invention is simple, and reaction is carried out in atmospheric conditions, and easy handling controls.Pressure-controlling is not had in reactor.Do not need expensive utility appliance, facility investment in early stage expense is few, and in addition, institute's adding medicine price is lower, and obtained product economy is reasonable.
3, after xylogen connects sulfonic group, because sulfonic group causes blunt meta-orienting group, further sulfonation can be more difficult, and this is also the sulfonation reason that often sulfonation degree is not high under normal pressure.The present invention carries out condensation by other intermediates of a sulfonation, methylolated xylogen and highly sulfonated, the overall sulfonation degree of product can be improved, last polycondensation condition is suitable in addition, and the additive dispersion effect of gained is good, and made water coal slurry concentration is high, good fluidity.
4, other intermediates of a sulfonation, methylolated xylogen and highly sulfonated are carried out condensation, not only the mobility of overall sulfonation degree and coal water slurry improves, and save the good stability of xylogen and the low advantage of cost, be a kind of efficiently excellent slurries additive agent.Processing parameter draws through experiment, because select water to make solvent, therefore temperature is lower than 100 DEG C, and raw material mainly selects alkali lignin, cheap, and proportioning is optimum range, and the additive effect prepared is better.This technological equipment investment is low, and flow process is also comparatively simple.
5, the CN102585940A patent in background technology is mixed with sulfonated acetone thing by sulfomethylation alkali lignin to add formaldehyde solution again, in experiment, temperature controls not good rear easy production precipitation, and formaldehyde is easy and in sulfomethylation, residual formaldehyde (as phenyl aldehyde) reacts, and causes wastage of material.And the present invention first allows formaldehyde and sulfonated acetone thing (intermediate product A) react, take full advantage of formaldehyde, ensure that reaction effect, and reaction process can not produce precipitation.
6, the CN102585940A patent in background technology is reacted successively in same reactor class, and total reaction time is 7-16 hour.And the present invention is proceed step by step, synthesis sulfonated acetone, formaldehyde intermediate product while synthesis sulfomethylation alkali lignin, total reaction time is 3-5 hour, significantly improves production efficiency.
Accompanying drawing explanation
Fig. 1 is the GPC comparison diagram of example product 19 and alkali lignin.
Embodiment
embodiment 1
A kind of Lignins slurries additive agent, comprises the following raw material according to weight parts:
The alkali lignin aqueous solution 200 parts
Sulphonating agent I 10 parts
Sulphonating agent II 50 parts
Ketone thing 50 parts
Aldehydes 100 parts
150 parts, water;
Described sulphonating agent I and sulphonating agent II is one or more the mixture in S-WAT, sodium bisulfite, Sodium Pyrosulfite, Sulfothiorine, thionamic acid, thionamic acid sodium; Described ketone thing is one or more the mixture in acetone, ketene, methyl phenyl ketone, methyl ethyl diketone, pimelinketone; Described aldehydes is the mixture of one or both arbitrary proportions of formalin, acetaldehyde solution.
embodiment 2
A kind of Lignins slurries additive agent, comprises the following raw material according to weight parts:
The alkali lignin aqueous solution 300 parts
Sulphonating agent I 20 parts
Sulphonating agent II 90 parts
Ketone thing 140 parts
Aldehydes 200 parts
250 parts, water;
Described sulphonating agent I and sulphonating agent II is one or more the mixture in S-WAT, sodium bisulfite, Sodium Pyrosulfite, Sulfothiorine, thionamic acid, thionamic acid sodium; Described ketone thing is one or more the mixture in acetone, ketene, methyl phenyl ketone, methyl ethyl diketone, pimelinketone; Described aldehydes is the mixture of one or both arbitrary proportions of formalin, acetaldehyde solution.
embodiment 3
A kind of Lignins slurries additive agent, comprises the following raw material according to weight parts:
The alkali lignin aqueous solution 250 parts
Sulphonating agent I 15 parts
Sulphonating agent II 70 parts
Ketone thing 95 parts
Aldehydes 150 parts
200 parts, water;
Described sulphonating agent I and sulphonating agent II is one or more the mixture in S-WAT, sodium bisulfite, Sodium Pyrosulfite, Sulfothiorine, thionamic acid, thionamic acid sodium; Described ketone thing is one or more the mixture in acetone, ketene, methyl phenyl ketone, methyl ethyl diketone, pimelinketone; Described aldehydes is the mixture of one or both arbitrary proportions of formalin, acetaldehyde solution.
embodiment 4
A kind of Lignins slurries additive agent, comprises the following raw material according to weight parts:
The alkali lignin aqueous solution 211 parts
Sulphonating agent I 12 parts
Sulphonating agent II 88 parts
Ketone thing 120 parts
Aldehydes 187 parts
230 parts, water;
Described sulphonating agent I and sulphonating agent II is one or more the mixture in S-WAT, sodium bisulfite, Sodium Pyrosulfite, Sulfothiorine, thionamic acid, thionamic acid sodium; Described ketone thing is one or more the mixture in acetone, ketene, methyl phenyl ketone, methyl ethyl diketone, pimelinketone; Described aldehydes is the mixture of one or both arbitrary proportions of formalin, acetaldehyde solution.
embodiment 5
On the basis of embodiment 1-4:
Preferably, described sulphonating agent I and sulphonating agent II be multiple mixture or wherein a kind of sulphonating agent is multiple mixture time, if containing S-WAT, so the mol ratio of S-WAT and other compound summations is >=1:1, and the mol ratio between other compounds is arbitrary proportion; If not containing S-WAT, the mol ratio so between other compounds is arbitrary proportion.
Preferably, when described ketone thing is multiple mixture, if containing acetone, so the mol ratio of acetone and other compound summations is >=3:2, and the mol ratio between other compounds is arbitrary proportion; If not containing acetone, the mol ratio so between other compounds is arbitrary proportion.
Preferably or further, described ketone thing is acetone.
Preferably, the concentration of described formaldehyde solution is the aqueous solution of 30%, acetaldehyde solution to be concentration be 35% the aqueous solution.
Preferably or further, described aldehydes is formaldehyde solution.
embodiment 6
On the basis of embodiment 1-4:
Preferably, described sulphonating agent I and sulphonating agent II be multiple mixture or wherein a kind of sulphonating agent is multiple mixture time, if containing S-WAT, so the mol ratio of S-WAT and other compound summations is >=1:1, and the mol ratio between other compounds is arbitrary proportion; If not containing S-WAT, the mol ratio so between other compounds is arbitrary proportion.
Preferably, when described ketone thing is multiple mixture, if containing acetone, so the mol ratio of acetone and other compound summations is >=3:2, and the mol ratio between other compounds is arbitrary proportion; If not containing acetone, the mol ratio so between other compounds is arbitrary proportion.
Preferably or further, described ketone thing is acetone.
Preferably, the concentration of described formaldehyde solution is the aqueous solution of 40%, acetaldehyde solution to be concentration be 40% the aqueous solution.
Preferably or further, described aldehydes is formaldehyde solution.
embodiment 7
On the basis of embodiment 1-4:
Preferably, described sulphonating agent I and sulphonating agent II be multiple mixture or wherein a kind of sulphonating agent is multiple mixture time, if containing S-WAT, so the mol ratio of S-WAT and other compound summations is >=1:1, and the mol ratio between other compounds is arbitrary proportion; If not containing S-WAT, the mol ratio so between other compounds is arbitrary proportion.
Preferably, when described ketone thing is multiple mixture, if containing acetone, so the mol ratio of acetone and other compound summations is >=3:2, and the mol ratio between other compounds is arbitrary proportion; If not containing acetone, the mol ratio so between other compounds is arbitrary proportion.
Preferably or further, described ketone thing is acetone.
Preferably, the concentration of described formaldehyde solution is the aqueous solution of 35%, acetaldehyde solution to be concentration be 37.5% the aqueous solution.
Preferably or further, described aldehydes is formaldehyde solution.
embodiment 8
On the basis of embodiment 1-4:
Preferably, described sulphonating agent I and sulphonating agent II be multiple mixture or wherein a kind of sulphonating agent is multiple mixture time, if containing S-WAT, so the mol ratio of S-WAT and other compound summations is >=1:1, and the mol ratio between other compounds is arbitrary proportion; If not containing S-WAT, the mol ratio so between other compounds is arbitrary proportion.
Preferably, when described ketone thing is multiple mixture, if containing acetone, so the mol ratio of acetone and other compound summations is >=3:2, and the mol ratio between other compounds is arbitrary proportion; If not containing acetone, the mol ratio so between other compounds is arbitrary proportion.
Preferably or further, described ketone thing is acetone.
Preferably, the concentration of described formaldehyde solution is the aqueous solution of 32%, acetaldehyde solution to be concentration be 39% the aqueous solution.
Preferably or further, described aldehydes is formaldehyde solution.
embodiment 9
A preparation method for Lignins slurries additive agent, comprises following processing step:
A, preparation quality mark are the alkali lignin aqueous solution of 25%;
B, get sulphonating agent I and part aldehydes, stir, add the alkali lignin aqueous solution, react 2h at temperature is 80 DEG C after, obtain intermediate product A, stand-by.
C, to get sulphonating agent II soluble in water, after hydrolysis for some time, adds ketone thing, at temperature is 45 DEG C, reacts 0.5h; Drip remaining aldehydes wherein again, after dropwising, add stand-by intermediate product A more wherein, after mixing at 75 DEG C isothermal reaction 1h, obtain sorrel liquid product and Lignins slurries additive agent of the present invention.
embodiment 10
A preparation method for Lignins slurries additive agent, comprises following processing step:
A, preparation quality mark are the alkali lignin aqueous solution of 45%;
B, get sulphonating agent I and part aldehydes, stir, add the alkali lignin aqueous solution, react 3h at temperature is 90 DEG C after, obtain intermediate product A, stand-by.
C, to get sulphonating agent II soluble in water, after hydrolysis for some time, adds ketone thing, at temperature is 55 DEG C, reacts 1.5h; Drip remaining aldehydes wherein again, after dropwising, add stand-by intermediate product A more wherein, after mixing at 85 DEG C isothermal reaction 2h, obtain sorrel liquid product and Lignins slurries additive agent of the present invention.
embodiment 11
A preparation method for Lignins slurries additive agent, comprises following processing step:
A, preparation quality mark are the alkali lignin aqueous solution of 35%;
B, get sulphonating agent I and part aldehydes, stir, add the alkali lignin aqueous solution, react 2.5h at temperature is 85 DEG C after, obtain intermediate product A, stand-by.
C, to get sulphonating agent II soluble in water, after hydrolysis for some time, adds ketone thing, at temperature is 50 DEG C, reacts 1h; Drip remaining aldehydes wherein again, after dropwising, add stand-by intermediate product A more wherein, after mixing at 80 DEG C isothermal reaction 1.5h, obtain sorrel liquid product and Lignins slurries additive agent of the present invention.
embodiment 12
A preparation method for Lignins slurries additive agent, comprises following processing step:
A, preparation quality mark are the alkali lignin aqueous solution of 42%;
B, get sulphonating agent I and part aldehydes, stir, add the alkali lignin aqueous solution, react 2.25h at temperature is 82 DEG C after, obtain intermediate product A, stand-by.
C, to get sulphonating agent II soluble in water, after hydrolysis for some time, adds ketone thing, at temperature is 54 DEG C, reacts 1.25h; Drip remaining aldehydes wherein again, after dropwising, add stand-by intermediate product A more wherein, after mixing at 76 DEG C isothermal reaction 1.75h, obtain sorrel liquid product and Lignins slurries additive agent of the present invention.
embodiment 13
On the basis of embodiment 9-12, preferred:
In step B and step C, the mass ratio of the aldehydes in described step B and the aldehydes in step C is 1:2.5.
In step C, described hydrolysis for some time refers to hydrolysis 10 minutes.
In step C, the remaining aldehydes of described dropping refers to and to drip off in 0.5h.
embodiment 14
On the basis of embodiment 9-12, preferred:
In step B and step C, the mass ratio of the aldehydes in described step B and the aldehydes in step C is 1:4.5.
In step C, described hydrolysis for some time refers to hydrolysis 45 minutes.
In step C, the remaining aldehydes of described dropping refers to and to drip off in 1h.
embodiment 15
On the basis of embodiment 9-12, preferred:
In step B and step C, the mass ratio of the aldehydes in described step B and the aldehydes in step C is 1:3.5.
In step C, described hydrolysis for some time refers to hydrolysis 27.5 minutes.
In step C, the remaining aldehydes of described dropping refers to and to drip off in 0.75h.
embodiment 16
On the basis of embodiment 9-12, preferred:
In step B and step C, the mass ratio of the aldehydes in described step B and the aldehydes in step C is 1:4.
In step C, described hydrolysis for some time refers to hydrolysis 30 minutes.
In step C, the remaining aldehydes of described dropping refers to and to drip off in 0.8h.
embodiment 17
Coal sample source place: Tongzi
Coal analysis is as follows:
Addictive preparation method:
Get the formaldehyde solution 20g of 37%, 15g S-WAT and 10g water, add the alkali lignin solution 250g that massfraction is 40%, stir, controlling temperature of reaction is 85 DEG C, and hydroxymethylation 2 hours, obtains intermediate product; In another reactor, add Sodium Pyrosulfite 83g, add 150g water, controlling temperature of reaction is 50 DEG C, be hydrolyzed 0.5 hour, add methyl phenyl ketone 121g, continue reaction 0.5 hour, then dripping concentration is the acetaldehyde solution 200g of 40%, controlling temperature of reaction is 75 DEG C, react 1 hour, add stand-by intermediate product, and be warmed up to 85 DEG C, react 2 hours, obtain sorrel liquid product.
Coal water slurry pulping effect: (target slurry concentration 69%)
Coal 100g, the consumption (butt) of slurries additive agent accounts for 0.35% of the quality of coal, the measured concentration 68.1%, 100S of coal water slurry
-1lower Cws Viscosity is 837mPas, and range estimation mobility is A.
embodiment 18
Coal sample source place: the Huang Jue village
Coal analysis is as follows:
Addictive preparation method:
Get the acetaldehyde solution 32.27g of 40%, 19.6g Sodium Pyrosulfite and 12g water, add the alkali lignin solution 280g that massfraction is 38.5%, stir, controlling temperature of reaction is 90 DEG C, and hydroxymethylation 2.5 hours, obtains intermediate product; In another reactor, add S-WAT 65.8g, add 135g water, controlling temperature of reaction is 50 DEG C, be hydrolyzed 0.5 hour, add methyl phenyl ketone 129g, continue reaction 0.5 hour, then dripping concentration is the formaldehyde solution 150g of 37%, controlling temperature of reaction is 75 DEG C, react 1 hour, add stand-by intermediate product, and be warmed up to 85 DEG C, react 3 hours, obtain sorrel liquid product.
Coal water slurry pulping effect: (target slurry concentration 69%)
Coal 100g, the consumption of slurries additive agent accounts for 0.35% of the quality of coal, the measured concentration 67.9%, 100S of coal water slurry
-1lower Cws Viscosity is 793mPas, and range estimation mobility is A.
embodiment 19
Coal sample source place: Guangan
Addictive preparation method:
Get the formaldehyde solution 18.81g of 37%, 11.8g sodium bisulfite and 10g water, add the alkali lignin solution 260g that massfraction is 39.5%, stir, controlling temperature of reaction is 85 DEG C, and hydroxymethylation 2.5 hours, obtains intermediate product; In another reactor, add S-WAT 61.5g, add 130g water, controlling temperature of reaction is 45 DEG C, be hydrolyzed 0.5 hour, add acetone 55g, continue reaction 0.5 hour, then dripping concentration is the formaldehyde solution 130g of 37%, controlling temperature of reaction is 70 DEG C, react 1 hour, add stand-by intermediate product, and be warmed up to 80 DEG C, react 3 hours, obtain sorrel liquid product.
Coal water slurry pulping effect: (target slurry concentration 69%)
Coal 100g, the consumption of slurries additive agent accounts for 0.35% of the quality of coal, the measured concentration 68.2%, 100S of coal water slurry
-1lower Cws Viscosity is 736mPas, and range estimation mobility is A.
embodiment 20
Coal sample source place: Tongzi
Addictive preparation method:
Get the formaldehyde solution 18g of 37%, 14.12g sodium bisulfite and 15g water, add the alkali lignin solution 240g that massfraction is 40%, stir, controlling temperature of reaction is 90 DEG C, and hydroxymethylation 2 hours, obtains intermediate product; In another reactor, add Sodium Pyrosulfite 85.21g, add 160g water, controlling temperature of reaction is 55 DEG C, be hydrolyzed 0.5 hour, add acetone 60g, continue reaction 0.5 hour, then dripping concentration is the acetaldehyde solution 190g of 40%, controlling temperature of reaction is 70 DEG C, react 1.5 hours, add stand-by intermediate product, and be warmed up to 85 DEG C, react 2.5 hours, obtain sorrel liquid product.
Coal water slurry pulping effect: (target slurry concentration 69%)
Coal 100g, the consumption of slurries additive agent accounts for 0.4% of the quality of coal, the measured concentration 67.8%, 100S of coal water slurry
-1lower Cws Viscosity is 803mPas, and range estimation mobility is A.
embodiment 21
The product of embodiment 17 and 19 and alkali lignin and other market products are carried out to the mensuration of sulfonation degree and contrast Tongzi coal viscosity in aqueous coal slurries test experiments, and addition is 0.4% of coal butt, the results are shown in Table 1.
Mobility: A is continuous flow; B is discontinuous flow; C is for flowing.
Table 1 is the Performance comparision of embodiment product and other market products, can find out that the sulfonation degree of this product is higher by data in table.Under identical Pulping conditions, the apparent viscosity of the made slurry of embodiment 19 product is minimum, and its fluidity of slurry is also better than other products.
embodiment 22
Fig. 1 shows embodiment 19 product and the difference of alkali lignin on average molecular mass.As seen from the figure, compared with alkali lignin, the average weight-molecular mass of embodiment 19 product is comparatively large, it can thus be appreciated that alkali lignin is after modified test, and relative molecular mass has increase by a relatively large margin.Simultaneously according to pulping test-results and GPC, illustrates in the process that product increases at relative molecular mass and introduce other polar groups, the increase of hydrophilic radical total amount, improves the hydrophilic-lipophilic balance of dispersant molecule, makes it better to the dispersion effect of coal water slurry.
Claims (8)
1. a Lignins slurries additive agent, is characterized in that: comprise the following raw material according to weight parts:
Alkali lignin aqueous solution 200-300 part
Sulphonating agent I 10-20 part
Sulphonating agent II 50-90 part
Ketone thing 50-140 part
Aldehydes 100-200 part
Water 150-250 part;
Described sulphonating agent I and sulphonating agent II is one or more the mixture in S-WAT, sodium bisulfite, Sodium Pyrosulfite, Sulfothiorine, thionamic acid, thionamic acid sodium; Described ketone thing is one or more the mixture in acetone, ketene, methyl phenyl ketone, methyl ethyl diketone, pimelinketone; Described aldehydes is the mixture of one or both arbitrary proportions of formalin, acetaldehyde solution;
Described Lignins slurries additive agent is obtained by following methods:
A, preparation quality mark are the alkali lignin aqueous solution of 25-45%;
B, get sulphonating agent I and part aldehydes, stir, add the alkali lignin aqueous solution, react 2-3h at temperature is 80-90 DEG C after, obtain intermediate product A, stand-by;
C, to get sulphonating agent II soluble in water, after hydrolysis for some time, adds ketone thing, at temperature is 45-55 DEG C, reacts 0.5-1.5h; Drip remaining aldehydes wherein again, the mass ratio of the part aldehydes in described step B and the remaining aldehydes in step C is 1:2.5-4.5; Add stand-by intermediate product A more wherein after dropwising, after mixing at 75-85 DEG C isothermal reaction 1-2h, obtain sorrel liquid product and Lignins slurries additive agent of the present invention.
2. a kind of Lignins slurries additive agent according to claim 1, it is characterized in that: described sulphonating agent I and sulphonating agent II be multiple mixture or wherein a kind of sulphonating agent is multiple mixture time, if containing S-WAT, so the mol ratio of S-WAT and other compound summations is >=1:1, and the mol ratio between other compounds is arbitrary proportion; If not containing S-WAT, the mol ratio so between other compounds is arbitrary proportion.
3. a kind of Lignins slurries additive agent according to claim 1, it is characterized in that: when described ketone thing is multiple mixture, if containing acetone, so the mol ratio of acetone and other compound summations is >=3:2, and the mol ratio between other compounds is arbitrary proportion; If not containing acetone, the mol ratio so between other compounds is arbitrary proportion.
4. a kind of Lignins slurries additive agent according to claim 1 or 3, is characterized in that: described ketone thing is acetone.
5. a kind of Lignins slurries additive agent according to claim 1, is characterized in that: the concentration of described formaldehyde solution is the aqueous solution of 30-40%, the aqueous solution of acetaldehyde solution to be concentration be 35-40%.
6. a kind of Lignins slurries additive agent according to claim 1 or 5, is characterized in that: described aldehydes is formaldehyde solution.
7. a kind of Lignins slurries additive agent according to claim 1, is characterized in that: in step C, and described hydrolysis for some time refers to hydrolysis 10-45 minute.
8. a kind of Lignins slurries additive agent according to claim 1, is characterized in that: in step C, and the remaining aldehydes of described dropping refers to and to drip off in 0.5-1h.
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| CN108441272A (en) * | 2018-04-16 | 2018-08-24 | 李智 | A kind of slurries additive agent and preparation method thereof |
| CN110791350B (en) * | 2018-08-01 | 2021-05-04 | 四川天法科技有限公司 | Biomass fuel slurry and preparation method thereof |
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| CN101225336A (en) * | 2008-02-01 | 2008-07-23 | 福州大学 | Alkali lignin-sulphonated acetone formaldehyde polycondensates coal water slurry additive and preparation method thereof |
| CN101322927A (en) * | 2008-07-29 | 2008-12-17 | 华南理工大学 | Coal water slurry dispersing agent made from black-liquor of straw pulping in paper-making and preparation thereof |
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