CN109897186B - Beta-cyclodextrin modified lignosulfonate, preparation method and application thereof, and preparation method of coal water slurry - Google Patents
Beta-cyclodextrin modified lignosulfonate, preparation method and application thereof, and preparation method of coal water slurry Download PDFInfo
- Publication number
- CN109897186B CN109897186B CN201711310975.4A CN201711310975A CN109897186B CN 109897186 B CN109897186 B CN 109897186B CN 201711310975 A CN201711310975 A CN 201711310975A CN 109897186 B CN109897186 B CN 109897186B
- Authority
- CN
- China
- Prior art keywords
- beta
- cyclodextrin
- lignosulfonate
- modified
- coal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229920000858 Cyclodextrin Polymers 0.000 title claims abstract description 134
- 239000001116 FEMA 4028 Substances 0.000 title claims abstract description 134
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 title claims abstract description 134
- 235000011175 beta-cyclodextrine Nutrition 0.000 title claims abstract description 134
- 229960004853 betadex Drugs 0.000 title claims abstract description 134
- 229920001732 Lignosulfonate Polymers 0.000 title claims abstract description 119
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 239000003245 coal Substances 0.000 title claims abstract description 48
- 239000002002 slurry Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000002270 dispersing agent Substances 0.000 claims abstract description 33
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000012986 modification Methods 0.000 claims abstract description 12
- 230000004048 modification Effects 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 239000003250 coal slurry Substances 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 229920005552 sodium lignosulfonate Polymers 0.000 claims description 8
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 7
- 239000003125 aqueous solvent Substances 0.000 claims description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 238000004537 pulping Methods 0.000 claims description 5
- 229920005551 calcium lignosulfonate Polymers 0.000 claims description 4
- 229920005550 ammonium lignosulfonate Polymers 0.000 claims description 3
- RYAGRZNBULDMBW-UHFFFAOYSA-L calcium;3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Ca+2].COC1=CC=CC(CC(CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O RYAGRZNBULDMBW-UHFFFAOYSA-L 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 229920005610 lignin Polymers 0.000 description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000001556 precipitation Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 239000003513 alkali Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000000654 additive Substances 0.000 description 4
- 238000007385 chemical modification Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000004321 preservation Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000003077 lignite Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000001694 spray drying Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 150000007514 bases Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 description 1
- 239000003830 anthracite Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002802 bituminous coal Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007547 defect Effects 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
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- NVVZQXQBYZPMLJ-UHFFFAOYSA-N formaldehyde;naphthalene-1-sulfonic acid Chemical compound O=C.C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 NVVZQXQBYZPMLJ-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 150000003385 sodium Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Abstract
The invention relates to the field of preparation of coal water slurry, in particular to beta-cyclodextrin modified lignosulfonate, a preparation method and application thereof and a preparation method of coal water slurry. The beta-cyclodextrin modified lignosulfonate comprises a modifying group provided by beta-cyclodextrin, and the modifying group is connected with the lignosulfonate through a connecting chain provided by epichlorohydrin; wherein the beta-cyclodextrin modified lignosulfonate contains modification groups provided by beta-cyclodextrin in an amount of 5-25 [ mu ] mol per g of the beta-cyclodextrin modified lignosulfonate. The coal water slurry obtained by using the beta-cyclodextrin modified lignosulfonate as the dispersing agent has higher concentration, better fluidity and stability.
Description
Technical Field
The invention relates to the field of preparation of coal water slurry, in particular to beta-cyclodextrin modified lignosulfonate, a preparation method and application thereof and a preparation method of coal water slurry.
Background
Coal water slurry is a raw material of a coal water slurry gasification furnace in coal chemical industry, billions of tons of coal water slurry are consumed in China every year, factors influencing the performance and the production cost of the coal water slurry mainly comprise raw material coal, additives and a pulping process, and the pulping process and the raw material coal are determined for a specific factory, so that the price and the performance of the additives are the second major factors influencing the cost of the coal water slurry. The dispersant is the main component of the coal water slurry additive, and the efficient coal water slurry dispersant with low cost, high dispersivity and high stability is the key field of coal water slurry research.
Lignosulfonate derived from papermaking waste liquid is widely used in industries such as coal water slurry additives, cement water reducing agents and the like as a dispersing agent due to surface activity, but has large use amount and poor viscosity reducing effect due to wide molecular weight distribution and complex structure. In the art, lignosulfonates can be modified by several methods:
(1) the performance of the lignin dispersing agent can be enhanced by physically separating and removing ash, saccharides and other small molecular impurities in the lignin dispersing agent, and the sodium lignosulfonate with the molecular weight of 10000-50000 is obtained by ultrafiltration classification, wherein the sodium lignosulfonate with the molecular weight range has the best dispersion viscosity reduction effect.
(2) The composite can be compounded with other dispersants, such as nonionic surfactant, naphthalene sulfonic acid formaldehyde polycondensate and polycarboxylic acid, although the performance of the coal water slurry can be obviously improved and the application range of the lignin system can be enlarged, the price of the dispersant compounded with the composite is higher than that of the lignin system, so that the price of the composite is higher, and the structure and the surface performance of the lignin dispersant are not fundamentally changed as the physical separation is.
(3) Chemical modification method: the molecular structure of lignin contains active groups such as carbonyl, phenolic hydroxyl, alcoholic hydroxyl and the like, and functional groups or structures which are beneficial to improving the dispersibility can be easily introduced into lignin molecules through chemical reactions, for example, the content of hydroxyl is increased by using an oxidation reaction, the number of sulfonate groups is increased by using a sulfonation reaction, the molecular weight is increased by using a polycondensation reaction, and the molecular structure with carboxyl is introduced by using graft copolymerization. The chemical modification methods obtain the lignin dispersing agent with good dispersibility and stability by changing the molecular structure of lignin, and can prepare the coal water slurry with excellent performance, so the chemical modification is an effective way for preparing the lignin dispersing agent with high performance, low cost and wide adaptability. Among them, research and research for improving the properties of lignin-based dispersions by chemical modification has never been interrupted.
CN106397688A discloses a polymer modified lignin derivative obtained by using acrylic acid, methacrylic acid and hydroxyethyl acrylate as modifiers and lignin, which has better steric hindrance effect and better dispersion effect than common sodium lignin sulfonate. However, the polymer-modified lignin derivative is suitable for the field of color dispersants, and for dispersants for coal water slurry dispersants, on the one hand, the cost is high, and the applicability in the field of coal water slurry is yet to be confirmed.
Disclosure of Invention
The invention aims to overcome the defect of poor dispersing effect of the existing water-coal-slurry dispersing agent, and provides beta-cyclodextrin modified lignosulfonate with excellent dispersing effect when used as the water-coal-slurry dispersing agent, a preparation method and application thereof, and a preparation method of water-coal-slurry.
In order to achieve the above object, the present invention provides, in one aspect, a β -cyclodextrin-modified lignosulfonate comprising a modifying group provided by β -cyclodextrin, the modifying group and lignosulfonate being connected by a connecting chain provided by epichlorohydrin; wherein the beta-cyclodextrin modified lignosulfonate contains modification groups provided by beta-cyclodextrin in an amount of 5-25 [ mu ] mol per g of the beta-cyclodextrin modified lignosulfonate.
The second aspect of the present invention provides a method for preparing the above-mentioned β -cyclodextrin modified lignosulfonate, which comprises: in an aqueous solvent, under an alkaline condition, carrying out a first contact reaction on lignosulfonate and epoxy chloropropane; then introducing beta-cyclodextrin into the system of the first contact reaction, and carrying out a second contact reaction on the product of the first contact reaction and the beta-cyclodextrin; the lignosulfonate and the beta-cyclodextrin are used in amounts such that the beta-cyclodextrin modified lignosulfonate contains modification groups provided by the beta-cyclodextrin in an amount of 5-25 μmol per g of the beta-cyclodextrin modified lignosulfonate.
The third aspect of the invention provides an application of the beta-cyclodextrin modified lignosulfonate as a water-coal-slurry dispersing agent in preparation of water-coal-slurry.
The fourth aspect of the invention provides a preparation method of coal water slurry, which comprises the following steps: and pulping coal, a water-coal-slurry dispersing agent and water, wherein the water-coal-slurry dispersing agent contains the beta-cyclodextrin modified lignosulfonate.
The coal water slurry obtained by using the beta-cyclodextrin modified lignosulfonate as the dispersing agent has higher concentration, better fluidity and stability.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a beta-cyclodextrin modified lignosulfonate, which contains a modifying group provided by beta-cyclodextrin, wherein the modifying group and the lignosulfonate are connected through a connecting chain provided by epichlorohydrin; wherein the beta-cyclodextrin modified lignosulfonate contains modification groups provided by beta-cyclodextrin in an amount of 5-25 [ mu ] mol per g of the beta-cyclodextrin modified lignosulfonate.
According to the invention, the amount of the modifying group provided by beta-cyclodextrin contained in each g of the beta-cyclodextrin modified lignosulfonate is controlled to be 5-25 mu mol, so that the beta-cyclodextrin modified lignosulfonate can be used as a water-coal-slurry dispersing agent to obtain water-coal-slurry with better fluidity and more stability under higher coal content, and when the amount of the modifying group provided by beta-cyclodextrin contained in each g of the modified lignosulfonate is less than 5 mu mol, the water-coal-slurry has the problem of poor stability; when the amount of the modifying group provided by the beta-cyclodextrin is more than 25 [ mu ] mol per g of the beta-cyclodextrin modified lignosulfonate, the water solubility of the beta-cyclodextrin modified lignosulfonate itself is reduced, and the beta-cyclodextrin modified lignosulfonate cannot be effectively utilized. More preferably, the lignosulfonate and the beta-cyclodextrin are used in such amounts that the beta-cyclodextrin-modified lignosulfonate contains modifying groups provided by the beta-cyclodextrin in an amount of 10-20, preferably 12-16, mol per g of the beta-cyclodextrin-modified lignosulfonate.
According to the invention, the modified group and the lignosulfonate are connected through a connecting chain provided by epoxy chloropropane, wherein the epoxy chloropropane can react with the phenolic hydroxyl group of the lignosulfonate to be bonded under the condition of removing one molecule of HCl, so that the lignosulfonate is provided with an epoxy ring through an ether bond, and the hydroxyl group of the beta-cyclodextrin attacks the exposed carbon of the epoxy ring to open the epoxy ring and be connected through the ether bond.
According to the invention, the lignosulfonate has water solubility, the lignosulfonate of the invention can have various choices, and preferably the lignosulfonate is one or more of calcium lignosulfonate, sodium lignosulfonate, ammonium lignosulfonate, potassium lignosulfonate and magnesium lignosulfonate.
The second aspect of the present invention provides a method for preparing the above-mentioned β -cyclodextrin modified lignosulfonate, which comprises: in an aqueous solvent, under an alkaline condition, carrying out a first contact reaction on lignosulfonate and epoxy chloropropane; then introducing beta-cyclodextrin into the system of the first contact reaction, and carrying out a second contact reaction on the product of the first contact reaction and the beta-cyclodextrin; the lignosulfonate and the beta-cyclodextrin are used in amounts such that the beta-cyclodextrin modified lignosulfonate contains modification groups provided by the beta-cyclodextrin in an amount of 5-25 μmol per g of the beta-cyclodextrin modified lignosulfonate.
According to the invention, the lignosulfonate and the beta-cyclodextrin are preferably used in such amounts that the beta-cyclodextrin-modified lignosulfonate contains modification groups in an amount of 10 to 20 μmol, preferably 12 to 16 μmol, per g of the beta-cyclodextrin-modified lignosulfonate.
Under the condition of satisfying the above range, preferably, the lignosulfonate and the beta-cyclodextrin are used in a weight ratio of 100: 40-120, preferably 100: 50-100.
Preferably, the weight ratio of the usage amount of the lignosulfonate to the usage amount of the epichlorohydrin is 100: 20-100, preferably 100: 25-60.
According to the invention, the aqueous solvent may be water or an aqueous solution containing another solvent, preferably water. Wherein the amount of the aqueous solvent may vary within a wide range, preferably 500-3000 parts by weight relative to 100 parts by weight of the lignosulfonate. In the invention, the lignosulfonate and the aqueous solvent are mixed and then introduced into epichlorohydrin for the first contact reaction.
According to the invention, preferably, the alkaline conditions have a pH of between 10 and 12, more preferably between 11 and 12. The basic compound providing the basic condition is preferably one or more of sodium hydroxide, potassium hydroxide and lithium hydroxide. The basic compound may be provided in solid form or in the form of an aqueous solution, for example in the form of 10 to 30% by weight.
According to the invention, the conditions of the first contact reaction comprise: the temperature is 45-65 ℃ and the time is 1.5-4 h. Preferably, the conditions of the first contact reaction include: the temperature is 50-60 ℃ and the time is 2-4 h. Before the first contact reaction, the lignosulfonate and water can be mixed and heated to the problem of the first contact reaction, and then the pH is adjusted to be alkaline, and then the epichlorohydrin is introduced for the first contact reaction.
According to the present invention, the first contact reaction may be performed under an inert atmosphere, for example, under an atmosphere of one or more of nitrogen, argon, neon, and the like, and the above-mentioned gases may be introduced into the reaction system to maintain the inert atmosphere before introducing the epichlorohydrin.
According to the present invention, preferably, the conditions of the second contact reaction include: the temperature is 75-90 ℃ and the time is 2-5 h. More preferably, the conditions of the second contact reaction include: the temperature is 80-90 ℃ and the time is 2-4 h. Before the second contact reaction, the temperature of the reaction system is increased to the temperature of the second contact reaction, and then the beta-cyclodextrin is introduced. The beta-cyclodextrin can be provided in the form of an aqueous solution thereof, such as a 20-60 wt% aqueous solution of beta-cyclodextrin.
According to the present invention, in order to extract the β -cyclodextrin modified lignosulfonate, the above method of the present invention may further include: and adjusting the pH value of the reaction system after the second contact reaction to 7-8, then oxidizing calcium or other feasible substances to remove sulfate radicals, and filtering to remove the obtained sulfate, wherein the obtained color filter is an aqueous solution of the beta-cyclodextrin modified lignosulfonate, and the solid powder of the beta-cyclodextrin modified lignosulfonate can be obtained in a spray drying mode.
The third aspect of the invention provides an application of the beta-cyclodextrin modified lignosulfonate as a water-coal-slurry dispersing agent in preparation of water-coal-slurry.
The fourth aspect of the invention provides a preparation method of coal water slurry, which comprises the following steps: and pulping coal, a water-coal-slurry dispersing agent and water, wherein the water-coal-slurry dispersing agent contains the beta-cyclodextrin modified lignosulfonate.
According to the invention, the beta-cyclodextrin modified lignosulfonate can obtain excellent coal water slurry dispersing effect at a low dosage, and preferably, the beta-cyclodextrin modified lignosulfonate is used in an amount of 0.2-0.6 wt% based on the dry weight of coal. The beta-cyclodextrin modified lignosulfonate can disperse coal of various coals, such as one or more of lignite, bituminous coal, anthracite coal and the like.
The concentration of the obtained coal-water slurry can reach more than 57 wt%, preferably more than 62 wt%, more preferably more than 65 wt%.
The coal water slurry obtained by using the beta-cyclodextrin modified lignosulfonate as the dispersing agent has higher concentration, better fluidity and stability.
The present invention will be described in detail below by way of examples.
In the following example, the following examples are given,
the coal quality of the coal used is shown in table 1, and the particle size distribution is shown in table 2:
TABLE 1
Note: madAir drying of the base water, AdDry base ash content, VdafDry ashless base volatiles, FCdFixed carbon content on a dry basis, CdDry basis carbon content, HdDry basis hydrogen content, NdDry basis nitrogen content, St,dDry basis total sulfur.
TABLE 2
Note: the content refers to the weight percentage of lignite particles leaking through a given sieve to the total lignite particles.
Sodium lignosulfonate was purchased from the chemical company, Lingyu, Calif.
Calcium lignosulfonate was purchased from Ringyu chemical Co., Ltd, Calif.
Alkali lignin is available from Shandong Weili environmental protection science and technology, Inc.
Beta-cyclodextrin was purchased from Zhiyuan Biotech, Inc., Shandong, Bingzhou.
The amount of the modified group provided by the beta-cyclodextrin in the beta-cyclodextrin modified lignosulfonate is measured by an ultraviolet spectrophotometer and is compared with a concentration-absorbance standard curve of the beta-cyclodextrin to obtain the beta-cyclodextrin modified lignosulfonate.
Example 1
This example illustrates the beta-cyclodextrin modified lignosulfonate of the present invention and its preparation.
Dissolving 100g of sodium lignosulfonate in 1000g of water, heating to 50 ℃, introducing nitrogen, adjusting the pH of the solution to 10.5 by using solid sodium hydroxide, dropwise adding 50g of epoxy chloropropane (20 drops/min), and reacting at 50 ℃ for 2 hours in a heat preservation manner; then heating to 85 ℃, dropwise adding an aqueous solution of beta-cyclodextrin (100g of beta-cyclodextrin and 200g of water; 40 drops/min), and reacting for 3 hours at 85 ℃ with heat preservation; and after cooling, adding dilute hydrochloric acid to adjust the pH value to 7, adding 20g of calcium oxide to remove sulfate, filtering, and carrying out spray drying on the filtrate to obtain solid powder, namely the beta-cyclodextrin modified lignosulfonate, wherein the amount of modified groups provided by the beta-cyclodextrin in each g of beta-cyclodextrin modified lignosulfonate is 14 mu mol.
Example 2
This example illustrates the beta-cyclodextrin modified lignosulfonate of the present invention and its preparation.
Dissolving 100g of calcium lignosulphonate in 1200g of water, heating to 60 ℃, introducing nitrogen, adjusting the pH of the solution to 11 by using solid sodium hydroxide, dropwise adding 25g of epoxy chloropropane (15 drops/min), and reacting at 60 ℃ for 2.5 hours in a heat preservation manner; then heating to 90 ℃, dropwise adding a water solution of beta-cyclodextrin (50g of beta-cyclodextrin and 100g of water; 50 drops/min), and reacting for 2.5h at 90 ℃ with heat preservation; and (3) after cooling, adding dilute hydrochloric acid to adjust the pH value to 7, and performing spray drying to obtain solid powder, namely the beta-cyclodextrin modified lignosulfonate, wherein the amount of modified groups provided by the beta-cyclodextrin in each g of the beta-cyclodextrin modified lignosulfonate is 10 mu mol.
Example 3
This example illustrates the beta-cyclodextrin modified lignosulfonate of the present invention and its preparation.
The process according to example 1, except that epichlorohydrin is used in an amount of 80g and that beta-cyclodextrin is used in an amount of 120 g; finally obtaining the beta-cyclodextrin modified lignosulfonate, wherein the amount of the modifying groups provided by the beta-cyclodextrin contained in each g of the beta-cyclodextrin modified lignosulfonate is 25 mu mol.
Example 4
This example illustrates the beta-cyclodextrin modified lignosulfonate of the present invention and its preparation.
The process according to example 1, except that epichlorohydrin is used in an amount of 20g and β -cyclodextrin is used in an amount of 40 g; finally obtaining the beta-cyclodextrin modified lignosulfonate, wherein the amount of the modifying groups provided by the beta-cyclodextrin contained in each g of the beta-cyclodextrin modified lignosulfonate is 5 mu mol.
Comparative example 1
The process according to example 1, except that 10g of epichlorohydrin and 20g of β -cyclodextrin are used; finally obtaining the beta-cyclodextrin modified lignosulfonate, wherein each g of the beta-cyclodextrin modified lignosulfonate contains 2 mu mol of modified groups provided by beta-cyclodextrin.
Comparative example 2
The process of example 1, except that epichlorohydrin was used in an amount of 110g and beta-cyclodextrin was used in an amount of 120 g; finally obtaining the beta-cyclodextrin modified lignosulfonate, wherein the amount of the modifying groups provided by the beta-cyclodextrin contained in each g of the beta-cyclodextrin modified lignosulfonate is 30 mu mol.
Comparative example 3
The method described in example 1, except that an equal weight of alkali lignin was used instead of sodium lignosulfonate; finally obtaining the beta-cyclodextrin modified alkali lignin, wherein each g of the beta-cyclodextrin modified alkali lignin contains 12 mu mol of modified groups provided by the beta-cyclodextrin.
Example coal Water slurry
Respectively using the beta-cyclodextrin modified lignosulfonate, the beta-cyclodextrin modified alkali lignin, the unmodified sodium lignosulfonate, the unmodified ammonium lignosulfonate and the unmodified alkali lignin as water-coal-slurry dispersing agents (the addition amount of the dispersing agents is shown in table 3, and the weight of dry coal is taken as a reference) to prepare the water-coal-slurry together with coal (the type of the coal is shown in table 3) and water, wherein the addition amount of the water-coal-slurry dispersing agents is shown in table 3, and the apparent viscosity of the obtained water-coal-slurry is kept to be 1000mPa & s (normal temperature, 100 s)-1Measured at shear rate), the concentrations of the slurries obtained with different dispersants, water separation rates at different test times, flowability and stability are shown in table 3.
And the water precipitation rate is obtained by weighing the mass of supernatant after the coal water slurry is sealed and kept stand in the measuring cylinder for 48 hours, wherein the supernatant accounts for the mass percent of the coal water slurry.
Fluidity is obtained by visual inspection, wherein class A refers to uninterrupted flow, class B refers to interrupted flow and is dense, class C refers to interrupted flow and is thin paste, and class D refers to no flow.
The stability is tested by a rod inserting method, wherein A grade refers to no precipitation and no precipitation: the B grade refers to no precipitation or a small amount of soft precipitation and a small amount of water precipitation; grade C means there is water evolution and severe precipitation; the D grade means that the precipitation is hard and the slurry cannot be regenerated.
TABLE 3
As can be seen from the data in the table, the coal water slurry obtained by using the beta-cyclodextrin modified lignosulfonate of the invention as a dispersing agent has higher concentration, better fluidity and stability.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (18)
1. A lignosulfonate modified by beta-cyclodextrin, which is characterized in that the lignosulfonate modified by the beta-cyclodextrin contains a modifying group provided by the beta-cyclodextrin, and the modifying group is connected with the lignosulfonate by a connecting chain provided by epichlorohydrin; wherein the beta-cyclodextrin modified lignosulfonate contains modification groups provided by beta-cyclodextrin in an amount of 5-25 [ mu ] mol per g of the beta-cyclodextrin modified lignosulfonate.
2. The beta-cyclodextrin modified lignosulfonate of claim 1, wherein the beta-cyclodextrin modified lignosulfonate contains modifying groups provided by the beta-cyclodextrin in an amount of 10-20 μmol per g of the beta-cyclodextrin modified lignosulfonate.
3. The beta-cyclodextrin modified lignosulfonate of claim 2, wherein the beta-cyclodextrin modified lignosulfonate contains an amount of modifying groups provided by the beta-cyclodextrin per g of the beta-cyclodextrin modified lignosulfonate of 12-16 μmol.
4. The beta-cyclodextrin modified lignosulfonate of any one of claims 1-3, wherein the lignosulfonate is one or more of calcium lignosulfonate, sodium lignosulfonate, ammonium lignosulfonate, potassium lignosulfonate and magnesium lignosulfonate.
5. A method of preparing a β -cyclodextrin modified lignosulfonate according to any one of claims 1-4, comprising: in an aqueous solvent, under an alkaline condition, carrying out a first contact reaction on lignosulfonate and epoxy chloropropane; then introducing beta-cyclodextrin into the system of the first contact reaction, and carrying out a second contact reaction on the product of the first contact reaction and the beta-cyclodextrin; the lignosulfonate and the beta-cyclodextrin are used in amounts such that the beta-cyclodextrin modified lignosulfonate contains modification groups provided by the beta-cyclodextrin in an amount of 5-25 μmol per g of the beta-cyclodextrin modified lignosulfonate.
6. The production method according to claim 5, wherein the lignosulfonate and the beta-cyclodextrin are used in amounts such that the beta-cyclodextrin-modified lignosulfonate contains modification groups provided by the beta-cyclodextrin in an amount of 10 to 20 μmol per g thereof.
7. The production method according to claim 6, wherein the lignosulfonate and the beta-cyclodextrin are used in amounts such that the beta-cyclodextrin-modified lignosulfonate contains modification groups provided by the beta-cyclodextrin in an amount of 12 to 16 μmol per g thereof.
8. The production method according to any one of claims 5 to 7, wherein the lignosulfonate and the beta-cyclodextrin are used in a weight ratio of 100: 40-120.
9. The preparation method according to claim 8, wherein the lignosulfonate and the beta-cyclodextrin are used in a weight ratio of 100: 50-100.
10. The preparation process according to claim 8, wherein the lignosulfonate and epichlorohydrin are used in a weight ratio of 100: 20-100.
11. The preparation process according to claim 10, wherein the lignosulfonate and epichlorohydrin are used in a weight ratio of 100: 25-60.
12. The production method according to any one of claims 5 to 7 and 9 to 11, wherein the pH of the alkaline condition is 10 to 12; the alkaline conditions are provided by one or more of sodium hydroxide, potassium hydroxide and lithium hydroxide.
13. The production method as claimed in claim 12, wherein the aqueous solvent is used in an amount of 500-3000 parts by weight relative to 100 parts by weight of the lignosulfonate.
14. The production method according to claim 12, wherein the conditions of the first contact reaction include: the temperature is 45-65 ℃ and the time is 1.5-4 h.
15. The production method according to claim 12, wherein the conditions of the second contact reaction include: the temperature is 75-90 ℃ and the time is 2-5 h.
16. Use of a β -cyclodextrin modified lignosulfonate according to any one of claims 1 to 4 as a dispersant for coal water slurry in the preparation of a coal water slurry.
17. A preparation method of coal water slurry comprises the following steps: pulping coal, a water-coal-slurry dispersant and water, wherein the water-coal-slurry dispersant contains the beta-cyclodextrin modified lignosulfonate of any one of claims 1 to 4.
18. The method of claim 17, wherein the beta-cyclodextrin modified lignosulfonate is used in an amount of 0.2-0.6 wt% based on the dry weight of the coal.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711310975.4A CN109897186B (en) | 2017-12-11 | 2017-12-11 | Beta-cyclodextrin modified lignosulfonate, preparation method and application thereof, and preparation method of coal water slurry |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711310975.4A CN109897186B (en) | 2017-12-11 | 2017-12-11 | Beta-cyclodextrin modified lignosulfonate, preparation method and application thereof, and preparation method of coal water slurry |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109897186A CN109897186A (en) | 2019-06-18 |
| CN109897186B true CN109897186B (en) | 2021-07-13 |
Family
ID=66942587
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711310975.4A Active CN109897186B (en) | 2017-12-11 | 2017-12-11 | Beta-cyclodextrin modified lignosulfonate, preparation method and application thereof, and preparation method of coal water slurry |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109897186B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110819401A (en) * | 2019-11-19 | 2020-02-21 | 安徽鑫固环保股份有限公司 | Maltodextrin modified coal water slurry dispersing agent and synthetic method thereof |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1194802C (en) * | 2002-11-08 | 2005-03-30 | 华南理工大学 | Modified lignin sulfosalt dispersant of water coal slurry |
| CN100393735C (en) * | 2006-08-10 | 2008-06-11 | 东北林业大学 | Lignin-Based cyclodextrin ester multi-purpose sorbent preparation method |
| CN101543744B (en) * | 2009-04-03 | 2011-08-31 | 北京弘扬紫东环保科技有限公司 | Multi-component composite water-coal-slurry dispersant and application thereof |
| CN101624479B (en) * | 2009-08-13 | 2013-07-03 | 浙江万丰化工有限公司 | Preparation method of strong basicity resisting dispersion dye |
| JP6836906B2 (en) * | 2014-06-02 | 2021-03-03 | アナヴォ・テクノロジーズ，リミテッド・ライアビリティ・カンパニー | Modified biopolymers and methods of their production and use |
| CN105018160B (en) * | 2015-06-24 | 2017-08-11 | 济南圣泉集团股份有限公司 | Coal water slurry dispersing agent and its preparation method and application |
| JP2018135403A (en) * | 2015-07-08 | 2018-08-30 | 株式会社シクロケム | Liquid fuel and method of producing the same |
-
2017
- 2017-12-11 CN CN201711310975.4A patent/CN109897186B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN109897186A (en) | 2019-06-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhou et al. | Evaluation of treated black liquor used as dispersant of concentrated coal–water slurry | |
| CN101550369A (en) | Water-coal-slurry additive and preparation method thereof | |
| CN1194802C (en) | Modified lignin sulfosalt dispersant of water coal slurry | |
| CN102031168A (en) | Anionic-nonionic complex gasified coal water slurry additive | |
| CN109897186B (en) | Beta-cyclodextrin modified lignosulfonate, preparation method and application thereof, and preparation method of coal water slurry | |
| CN104152195A (en) | Amphoteric humate coal water slurry dispersant as well as preparation and application thereof | |
| CN102115520B (en) | Alkali lignin-phenol-sodium sulfanilate-formaldehyde polycondensate and preparation method thereof | |
| CN102337026A (en) | Preparation method of natural plant cellulose-modified PA6 composite material | |
| CN112812866A (en) | Coal water slurry, preparation method thereof and preparation method of synthesis gas | |
| CN103627455B (en) | A kind of composite coal-water fluid or water Jiao slurry additive and its preparation method and application | |
| CN101293631B (en) | Uses of water hyacinth | |
| EP1090095B1 (en) | Composition for manufacture of fuel briquettes | |
| CN102614809B (en) | Method for preparing dispersing-stabilizing agent by using papermaking sludge | |
| CN106635205B (en) | A kind of water-coal-slurry compound additive and its preparation method and application | |
| Hong et al. | Structure–Adsorption Behavior–Dispersion Property Relationship of Alkyl Chain Cross-Linked Lignosulfonate with Different Molecular Weights | |
| CN1138847C (en) | Humic acid additives for water-coal slurry and its preparing process | |
| CN102161923B (en) | Coal water slurry dispersing agent | |
| CN211394380U (en) | Fine sediment resource recycle system of coal gasification | |
| CN110564468B (en) | Environment-friendly coal water slurry additive and application thereof in preparation process of superfine-grinding high-concentration coal slurry in coal chemical industry | |
| CN113512448A (en) | Additive composition for coal water slurry | |
| CN112226254A (en) | Method for cooperatively treating waste circuit board and printing and dyeing wastewater | |
| CN109022074B (en) | Coal water slurry adopting discontinuous particle size distribution and preparation method thereof | |
| CN108587709B (en) | Method for preparing coal water slurry additive from waste mother liquor and reaction residues of 2-naphthol | |
| CN113845948A (en) | Coal water slurry additive for low-rank coal pulping and coal water slurry | |
| CN115261048B (en) | Method for coking by blending coal with lignin in papermaking black liquor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP03 | Change of name, title or address | ||
| CP03 | Change of name, title or address |
Address after: 100011 Beijing Dongcheng District, West Binhe Road, No. 22 Patentee after: CHINA ENERGY INVESTMENT Corp.,Ltd. Patentee after: Beijing low carbon clean energy Research Institute Address before: 100011 Shenhua building, 22 West Binhe Road, Dongcheng District, Beijing Patentee before: SHENHUA GROUP Corp.,Ltd. Patentee before: NATIONAL INSTITUTE OF CLEAN-AND-LOW-CARBON ENERGY |