CN103666606A - Lignin water coal slurry additive and preparation method thereof - Google Patents
Lignin water coal slurry additive and preparation method thereof Download PDFInfo
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- CN103666606A CN103666606A CN201310583078.6A CN201310583078A CN103666606A CN 103666606 A CN103666606 A CN 103666606A CN 201310583078 A CN201310583078 A CN 201310583078A CN 103666606 A CN103666606 A CN 103666606A
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- lignins
- aldehydes
- slurries additive
- additive agent
- acetone
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- 229920005610 lignin Polymers 0.000 title claims abstract description 83
- 230000000996 additive effect Effects 0.000 title claims abstract description 56
- 239000000654 additive Substances 0.000 title claims abstract description 55
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 239000003250 coal slurry Substances 0.000 title abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 78
- 150000001299 aldehydes Chemical class 0.000 claims abstract description 50
- 150000002576 ketones Chemical class 0.000 claims abstract description 32
- 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
- 239000002002 slurry Substances 0.000 claims description 65
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 56
- 239000003513 alkali Substances 0.000 claims description 46
- 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
- 239000007864 aqueous solution Substances 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
- 238000012545 processing 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
- 238000006277 sulfonation reaction Methods 0.000 abstract description 22
- 230000000694 effects Effects 0.000 abstract description 12
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 230000002153 concerted effect Effects 0.000 abstract description 2
- 239000003245 coal Substances 0.000 description 34
- 239000000047 product Substances 0.000 description 19
- 238000000034 method Methods 0.000 description 6
- 238000004537 pulping Methods 0.000 description 5
- 238000009736 wetting Methods 0.000 description 5
- 238000007031 hydroxymethylation reaction Methods 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 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
- 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
- 230000015572 biosynthetic process Effects 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
- 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
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
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Abstract
The invention relates to a lignin water coal slurry additive and a preparation method thereof, which belong to the technical field of water coal slurry production. The lignin water coal slurry additive comprises the following raw materials in parts by weight: 200-300 parts of lignin solution, 10-20 parts of sulfonating agent I, 50-90 parts of sulfonating agent II, 50-140 parts of ketone, 100-200 parts of aldehyde and 500-600 parts of water. By adopting the lignin water coal slurry additive provided by the invention, the hydrophilia and the sulfonation degree are improved, the water coal slurry prepared by using the additive is good in mobility, and moreover the formula of the additive utilizes the concerted reaction of multiple sulfonating agents, so that the sulfonating effect is highlighted.
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 alkali lignin after modification can be used as slurries additive agent, uses, and has effectively strengthened utilization of resources.
The sulfonation reaction that is modified as to alkali lignin the best.Because the reaction activity of alkali lignin is higher, activity is lower, and conventionally Direct Sulfonation reaction is all auxiliaryly to carry out just reaching higher sulfonation degree under such as conditions such as microwave radiations in High Temperature High Pressure or other.Industrial alkali lignin sodium sulfonate just under high-temperature pressure (120-200 ℃) carry out alkali lignin sulfonation, but facility investment in which early stage is larger, has also more complicated of press operation.
Patent CN101235055 " a kind of method of manufacturing sodium lignosulfonate " preparing product need to react at 125-145 ℃.
Patent CN101475604 " a kind of method of preparing highly sulfonated sodium lignosulfonate " has introduced synthetic at the auxiliary lower highly sulfonated sodium lignosulfonate of microwave radiation, but this mode present stage is difficult to realize industrialization promotion.And the quality product obtaining 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 " has introduced 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 " has introduced producing sulfonated lignin, first adds formaldehyde, then adds the dry product that obtains after sulphite reacting by heating.But the modified lignin resin obtaining with upper type be additive often wetting ability do not reach requirement, sulfonation degree is also on the low side.This is because xylogen bleed as slurries additive agent is too many, cause coal water slurry stir in bubble too many, mobility is not good.Some acidic ph modifier using during to lignin modification is too many, causes in product sodium sulphate content 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 ", this patent discloses 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 is reacted with a certain amount of formaldehyde and sulphonating agent, prepare sulfomethylation alkali lignin; Again by alkaline conditioner and sulphonating agent and acetone generation catalysis sulfonation reaction, obtain sulfonated acetone prepolymer, add again the sulfomethylation alkali lignin and the further polymerization reaction take place of formaldehyde solution that have prepared, the slurries additive agent that formation contains sulfonic group, hydroxyl and alkyl active group, has improved 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 and not to be subject to season, and region limits, is convenient to deposit and transport, and has realized the higher value application of xylogen.
Additive in above-mentioned patent exists acetone consumption large, and has used alkaline conditioner, causes cost to increase and slurries additive agent wetting ability is low, sulfonation degree is low, causes the not good problem of coal water slurry mobility; In addition, in preparation method in above-mentioned patent, be that sulfomethylation alkali lignin is mixed and adds formaldehyde solution again with sulfonated acetone thing, temperature is controlled not good rear easy production precipitation, and formaldehyde easily reacts with residual formaldehyde in sulfomethylation (as phenyl aldehyde), 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 not good problem of coal water slurry mobility, a kind of Lignins slurries additive agent is provided, has improved wetting ability and sulfonation degree, and can not cause coal water slurry mobility not good.
In order to achieve the above object, the technical solution used in the present invention is as follows:
A Lignins slurries additive agent, is characterized in that: comprise following according to the raw material of parts by weight meter:
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 are 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 and sulphonating agent II can be identical, also can be different.
Sulphonating agent I of the present invention and sulphonating agent II are multiple mixture or when wherein a kind of sulphonating agent is multiple mixture, if contain S-WAT, the mol ratio of S-WAT and other compound summations is >=1:1 so, and the mol ratio between other compounds is arbitrary proportion; If do not contain S-WAT, the mol ratio between other compounds is arbitrary proportion so.
When ketone thing of the present invention is multiple mixture, if contain acetone, the mol ratio of acetone and other compound summations is >=3:2 so, and the mol ratio between other compounds is arbitrary proportion; If do not contain acetone, the mol ratio between other compounds is arbitrary proportion so.
Ketone thing of the present invention is acetone.
The concentration of formaldehyde solution of the present invention is the aqueous solution of 30-40%, and acetaldehyde solution is that concentration is the aqueous solution of 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:
The alkali lignin aqueous solution that A, preparation quality mark are 25-45%;
B, get sulphonating agent I and part aldehydes, stir, add the alkali lignin aqueous solution, after temperature is to react 2-3h at 80-90 ℃, obtain intermediate product A, stand-by.
C, to get sulphonating agent II soluble in water, after hydrolysis for some time, adds ketone thing, in temperature, is to react 0.5-1.5h at 45-55 ℃; Drip wherein more remaining aldehydes, after dropwising, add wherein stand-by intermediate product A, after mixing at 75-85 ℃ isothermal reaction 1-2h, obtaining sorrel liquid product is 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 the aldehydes in described step B and 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 in 0.5-1h and drips off.
The present invention compared with prior art has following outstanding advantages:
1, Lignins slurries additive agent of the present invention has improved wetting ability and sulfonation degree, the coal water slurry good fluidity that adopts this additive to prepare, and in the formula of additive of the present invention, adopt the concerted reaction of multiple sulphonating agent, given prominence to sulfonation effect, material rate difference is 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.The applicable coal scope of additive of the present invention is wider, 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 under condition of normal pressure, and easy handling is controlled.In reactor, do not have pressure-controlling.Do not need expensive utility appliance, facility investment in early stage expense is few, and in addition, institute's adding medicine price is lower, makes product economy reasonable.
3, when xylogen connects after sulfonic group, because sulfonic group is to cause blunt meta-orienting group, further sulfonation meeting is more difficult, and this is also the sulfonation not high reason of sulfonation degree often under normal pressure.The present invention carries out condensation by other intermediates of a sulfonation, methylolated xylogen and highly sulfonated, can improve the whole sulfonation degree of product, 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 to condensation, not only the mobility of whole sulfonation degree and coal water slurry improves, and good stability and the low advantage of cost of having preserved xylogen, be a kind of efficient good slurries additive agent.Processing parameter through experiment draw because select water to make solvent, thus temperature lower than 100 ℃, raw material is mainly selected alkali lignin, cheap, proportioning is optimum range, the additive effect of preparing is better.This technological equipment investment is low, and flow process is also comparatively simple.
5, the CN102585940A patent in background technology is that sulfomethylation alkali lignin is mixed and adds formaldehyde solution again with sulfonated acetone thing, in experiment, temperature is controlled not good rear easy production precipitation, and formaldehyde easily reacts with residual formaldehyde in sulfomethylation (as phenyl aldehyde), causes wastage of material.And the present invention first allows formaldehyde react with sulfonated acetone thing (intermediate product A), take full advantage of formaldehyde, guaranteed reaction effect, and reaction process can not produced precipitation.
6, the CN102585940A patent in background technology is to react successively in same reactor class, and total reaction time is 7-16 hour.And the present invention is proceed step by step, synthetic sulfonated acetone, formaldehyde intermediate product in synthetic sulfomethylation alkali lignin, total reaction time is 3-5 hour, has obviously improved production efficiency.
Accompanying drawing explanation
Fig. 1 is the GPC comparison diagram of example product 19 and alkali lignin.
Embodiment
embodiment 1
A Lignins slurries additive agent, comprises following according to the raw material of parts by weight meter:
200 parts of the alkali lignin aqueous solution
10 parts of sulphonating agent I
50 parts of sulphonating agent II
50 parts of ketone things
100 parts of aldehydes
150 parts, water;
Described sulphonating agent I and sulphonating agent II are 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 Lignins slurries additive agent, comprises following according to the raw material of parts by weight meter:
300 parts of the alkali lignin aqueous solution
20 parts of sulphonating agent I
90 parts of sulphonating agent II
140 parts of ketone things
200 parts of aldehydes
250 parts, water;
Described sulphonating agent I and sulphonating agent II are 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 Lignins slurries additive agent, comprises following according to the raw material of parts by weight meter:
250 parts of the alkali lignin aqueous solution
15 parts of sulphonating agent I
70 parts of sulphonating agent II
95 parts of ketone things
150 parts of aldehydes
200 parts, water;
Described sulphonating agent I and sulphonating agent II are 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 Lignins slurries additive agent, comprises following according to the raw material of parts by weight meter:
211 parts of the alkali lignin aqueous solution
12 parts of sulphonating agent I
88 parts of sulphonating agent II
120 parts of ketone things
187 parts of aldehydes
230 parts, water;
Described sulphonating agent I and sulphonating agent II are 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 are multiple mixture or when wherein a kind of sulphonating agent is multiple mixture, if contain S-WAT, the mol ratio of S-WAT and other compound summations is >=1:1 so, and the mol ratio between other compounds is arbitrary proportion; If do not contain S-WAT, the mol ratio between other compounds is arbitrary proportion so.
Preferably, when described ketone thing is multiple mixture, if contain acetone, the mol ratio of acetone and other compound summations is >=3:2 so, and the mol ratio between other compounds is arbitrary proportion; If do not contain acetone, the mol ratio between other compounds is arbitrary proportion so.
Preferably or further, described ketone thing is acetone.
Preferably, the aqueous solution that the concentration of described formaldehyde solution is 30%, acetaldehyde solution is that concentration is 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 are multiple mixture or when wherein a kind of sulphonating agent is multiple mixture, if contain S-WAT, the mol ratio of S-WAT and other compound summations is >=1:1 so, and the mol ratio between other compounds is arbitrary proportion; If do not contain S-WAT, the mol ratio between other compounds is arbitrary proportion so.
Preferably, when described ketone thing is multiple mixture, if contain acetone, the mol ratio of acetone and other compound summations is >=3:2 so, and the mol ratio between other compounds is arbitrary proportion; If do not contain acetone, the mol ratio between other compounds is arbitrary proportion so.
Preferably or further, described ketone thing is acetone.
Preferably, the aqueous solution that the concentration of described formaldehyde solution is 40%, acetaldehyde solution is that concentration is 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 are multiple mixture or when wherein a kind of sulphonating agent is multiple mixture, if contain S-WAT, the mol ratio of S-WAT and other compound summations is >=1:1 so, and the mol ratio between other compounds is arbitrary proportion; If do not contain S-WAT, the mol ratio between other compounds is arbitrary proportion so.
Preferably, when described ketone thing is multiple mixture, if contain acetone, the mol ratio of acetone and other compound summations is >=3:2 so, and the mol ratio between other compounds is arbitrary proportion; If do not contain acetone, the mol ratio between other compounds is arbitrary proportion so.
Preferably or further, described ketone thing is acetone.
Preferably, the aqueous solution that the concentration of described formaldehyde solution is 35%, acetaldehyde solution is that concentration is 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 are multiple mixture or when wherein a kind of sulphonating agent is multiple mixture, if contain S-WAT, the mol ratio of S-WAT and other compound summations is >=1:1 so, and the mol ratio between other compounds is arbitrary proportion; If do not contain S-WAT, the mol ratio between other compounds is arbitrary proportion so.
Preferably, when described ketone thing is multiple mixture, if contain acetone, the mol ratio of acetone and other compound summations is >=3:2 so, and the mol ratio between other compounds is arbitrary proportion; If do not contain acetone, the mol ratio between other compounds is arbitrary proportion so.
Preferably or further, described ketone thing is acetone.
Preferably, the aqueous solution that the concentration of described formaldehyde solution is 32%, acetaldehyde solution is that concentration is 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:
The alkali lignin aqueous solution that A, preparation quality mark are 25%;
B, get sulphonating agent I and part aldehydes, stir, add the alkali lignin aqueous solution, after temperature is to react 2h at 80 ℃, obtain intermediate product A, stand-by.
C, to get sulphonating agent II soluble in water, after hydrolysis for some time, adds ketone thing, in temperature, is to react 0.5h at 45 ℃; Drip wherein more remaining aldehydes, after dropwising, add wherein more stand-by intermediate product A, after mixing at 75 ℃ isothermal reaction 1h, obtaining sorrel liquid product is Lignins slurries additive agent of the present invention.
embodiment 10
A preparation method for Lignins slurries additive agent, comprises following processing step:
The alkali lignin aqueous solution that A, preparation quality mark are 45%;
B, get sulphonating agent I and part aldehydes, stir, add the alkali lignin aqueous solution, after temperature is to react 3h at 90 ℃, obtain intermediate product A, stand-by.
C, to get sulphonating agent II soluble in water, after hydrolysis for some time, adds ketone thing, in temperature, is to react 1.5h at 55 ℃; Drip wherein more remaining aldehydes, after dropwising, add wherein more stand-by intermediate product A, after mixing at 85 ℃ isothermal reaction 2h, obtaining sorrel liquid product is Lignins slurries additive agent of the present invention.
embodiment 11
A preparation method for Lignins slurries additive agent, comprises following processing step:
The alkali lignin aqueous solution that A, preparation quality mark are 35%;
B, get sulphonating agent I and part aldehydes, stir, add the alkali lignin aqueous solution, after temperature is to react 2.5h at 85 ℃, obtain intermediate product A, stand-by.
C, to get sulphonating agent II soluble in water, after hydrolysis for some time, adds ketone thing, in temperature, is to react 1h at 50 ℃; Drip wherein more remaining aldehydes, after dropwising, add wherein more stand-by intermediate product A, after mixing at 80 ℃ isothermal reaction 1.5h, obtaining sorrel liquid product is Lignins slurries additive agent of the present invention.
embodiment 12
A preparation method for Lignins slurries additive agent, comprises following processing step:
The alkali lignin aqueous solution that A, preparation quality mark are 42%;
B, get sulphonating agent I and part aldehydes, stir, add the alkali lignin aqueous solution, after temperature is to react 2.25h at 82 ℃, obtain intermediate product A, stand-by.
C, to get sulphonating agent II soluble in water, after hydrolysis for some time, adds ketone thing, in temperature, is to react 1.25h at 54 ℃; Drip wherein more remaining aldehydes, after dropwising, add wherein more stand-by intermediate product A, after mixing at 76 ℃ isothermal reaction 1.75h, obtaining sorrel liquid product is 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 the aldehydes in described step B and 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 in 0.5h and drips off.
embodiment 14
On the basis of embodiment 9-12, preferred:
In step B and step C, the mass ratio of the aldehydes in the aldehydes in described step B and 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 in 1h and drips off.
embodiment 15
On the basis of embodiment 9-12, preferred:
In step B and step C, the mass ratio of the aldehydes in the aldehydes in described step B and 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 in 0.75h and drips off.
embodiment 16
On the basis of embodiment 9-12, preferred:
In step B and step C, the mass ratio of the aldehydes in the aldehydes in described step B and 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 in 0.8h and drips off.
embodiment 17
Coal sample source place: Tongzi
Coal analysis is as follows:
Addictive preparation method:
Get 37% formaldehyde solution 20g, 15g S-WAT and 10g water, adding massfraction is 40% alkali lignin solution 250g, stirs, and controlling temperature of reaction is 85 ℃, and hydroxymethylation 2 hours, obtains intermediate product; In another reactor, add Sodium Pyrosulfite 83g, add 150g water, controlling temperature of reaction is 50 ℃, be hydrolyzed 0.5 hour, add methyl phenyl ketone 121g, continue reaction 0.5 hour, then drip concentration and be 40% acetaldehyde solution 200g, controlling temperature of reaction is 75 ℃, react 1 hour, add stand-by intermediate product, and be warmed up to 85 ℃, react 2 hours, obtain sorrel liquid product.
Coal water slurry pulping effect: (target slurry concentration 69%)
Coal 100g, the consumption of slurries additive agent (butt) account for coal quality 0.35%, the measured concentration 68.1% of coal water slurry, 100S
-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 40% acetaldehyde solution 32.27g, 19.6g Sodium Pyrosulfite and 12g water, adding massfraction is 38.5% alkali lignin solution 280g, stirs, and controlling temperature of reaction is 90 ℃, 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 ℃, be hydrolyzed 0.5 hour, add methyl phenyl ketone 129g, continue reaction 0.5 hour, then drip concentration and be 37% formaldehyde solution 150g, controlling temperature of reaction is 75 ℃, react 1 hour, add stand-by intermediate product, and be warmed up to 85 ℃, react 3 hours, obtain sorrel liquid product.
Coal water slurry pulping effect: (target slurry concentration 69%)
Coal 100g, the consumption of slurries additive agent account for coal quality 0.35%, the measured concentration 67.9% of coal water slurry, 100S
-1lower Cws Viscosity is 793mPas, and range estimation mobility is A.
embodiment 19
Coal sample source place: Guangan
Addictive preparation method:
Get 37% formaldehyde solution 18.81g, 11.8g sodium bisulfite and 10g water, adding massfraction is 39.5% alkali lignin solution 260g, stirs, and controlling temperature of reaction is 85 ℃, 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 ℃, be hydrolyzed 0.5 hour, add acetone 55g, continue reaction 0.5 hour, then drip concentration and be 37% formaldehyde solution 130g, controlling temperature of reaction is 70 ℃, react 1 hour, add stand-by intermediate product, and be warmed up to 80 ℃, react 3 hours, obtain sorrel liquid product.
Coal water slurry pulping effect: (target slurry concentration 69%)
Coal 100g, the consumption of slurries additive agent account for coal quality 0.35%, the measured concentration 68.2% of coal water slurry, 100S
-1lower Cws Viscosity is 736mPas, and range estimation mobility is A.
embodiment 20
Coal sample source place: Tongzi
Addictive preparation method:
Get 37% formaldehyde solution 18g, 14.12g sodium bisulfite and 15g water, adding massfraction is 40% alkali lignin solution 240g, stirs, and controlling temperature of reaction is 90 ℃, and hydroxymethylation 2 hours, obtains intermediate product; In another reactor, add Sodium Pyrosulfite 85.21g, add 160g water, controlling temperature of reaction is 55 ℃, be hydrolyzed 0.5 hour, add acetone 60g, continue reaction 0.5 hour, then drip concentration and be 40% acetaldehyde solution 190g, controlling temperature of reaction is 70 ℃, react 1.5 hours, add stand-by intermediate product, and be warmed up to 85 ℃, 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 account for coal quality 0.4%, the measured concentration 67.8% of coal water slurry, 100S
-1lower Cws Viscosity is 803mPas, and range estimation mobility is A.
embodiment 21
To the product of embodiment 17 and 19 and alkali lignin and other market products carry out the mensuration of sulfonation degree and to the contrast of Tongzi coal viscosity in aqueous coal slurries test experiments, 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 be embodiment product and other market products Performance Ratio, by table in data can find out that the sulfonation degree of this product is higher.Under identical slurrying condition, 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 products and the difference of alkali lignin on average molecular mass.As seen from the figure, compare with alkali lignin, the average weight-molecular mass of embodiment 19 products is larger, and hence one can see that, and 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, illustrate in the process that product increases at relative molecular mass and introduced other polar groups, the increase of hydrophilic radical total amount, has improved the hydrophilic-lipophilic balance of dispersant molecule, makes its dispersion effect to coal water slurry better.
Claims (10)
1. a Lignins slurries additive agent, is characterized in that: comprise following according to the raw material of parts by weight meter:
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 are 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.
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 are multiple mixture or when wherein a kind of sulphonating agent is multiple mixture, if contain S-WAT, the mol ratio of S-WAT and other compound summations is >=1:1 so, and the mol ratio between other compounds is arbitrary proportion; If do not contain S-WAT, the mol ratio between other compounds is arbitrary proportion so.
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 contain acetone, the mol ratio of acetone and other compound summations is >=3:2 so, and the mol ratio between other compounds is arbitrary proportion; If do not contain acetone, the mol ratio between other compounds is arbitrary proportion so.
4. according to a kind of Lignins slurries additive agent described in claim 1 or 3, it 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 aqueous solution that the concentration of described formaldehyde solution is 30-40%, acetaldehyde solution is that concentration is the aqueous solution of 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. the preparation method of a kind of Lignins slurries additive agent according to claim 1, is characterized in that: comprise following processing step:
The alkali lignin aqueous solution that A, preparation quality mark are 25-45%;
B, get sulphonating agent I and part aldehydes, stir, add the alkali lignin aqueous solution, after temperature is to react 2-3h at 80-90 ℃, obtain intermediate product A, stand-by;
C, to get sulphonating agent II soluble in water, after hydrolysis for some time, adds ketone thing, in temperature, is to react 0.5-1.5h at 45-55 ℃; Drip wherein more remaining aldehydes, after dropwising, add wherein more stand-by intermediate product A, after mixing at 75-85 ℃ isothermal reaction 1-2h, obtaining sorrel liquid product is Lignins slurries additive agent of the present invention.
8. the preparation method of a kind of Lignins slurries additive agent according to claim 7, is characterized in that: in step B and step C, the mass ratio of the aldehydes in the aldehydes in described step B and step C is 1:2.5-4.5.
9. the preparation method of a kind of Lignins slurries additive agent according to claim 7, is characterized in that: in step C, described hydrolysis for some time refers to hydrolysis 10-45 minute.
10. the preparation method of a kind of Lignins slurries additive agent according to claim 7, is characterized in that: in step C, the remaining aldehydes of described dropping refers in 0.5-1h and drips off.
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| CN108441272A (en) * | 2018-04-16 | 2018-08-24 | 李智 | A kind of slurries additive agent and preparation method thereof |
| CN110791350A (en) * | 2018-08-01 | 2020-02-14 | 四川天法科技有限公司 | Biomass fuel slurry and preparation method thereof |
| CN113174024A (en) * | 2021-06-08 | 2021-07-27 | 吉林大学 | Preparation method of biomass phenolic resin |
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