CN111333859A - Aminated lignin and preparation method and application thereof - Google Patents
Aminated lignin and preparation method and application thereof Download PDFInfo
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- 229920005610 lignin Polymers 0.000 title claims abstract description 92
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 53
- 239000000243 solution Substances 0.000 claims abstract description 34
- 238000005576 amination reaction Methods 0.000 claims abstract description 28
- 239000007864 aqueous solution Substances 0.000 claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- 239000003513 alkali Substances 0.000 claims abstract description 14
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 238000005086 pumping Methods 0.000 claims abstract description 9
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 230000035484 reaction time Effects 0.000 claims abstract description 5
- 239000010426 asphalt Substances 0.000 claims description 35
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 8
- 239000003995 emulsifying agent Substances 0.000 claims description 7
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 238000007327 hydrogenolysis reaction Methods 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- -1 aliphatic amine compound Chemical class 0.000 claims description 3
- 238000004945 emulsification Methods 0.000 claims description 3
- 239000003381 stabilizer Substances 0.000 claims description 3
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 2
- 238000005984 hydrogenation reaction Methods 0.000 claims description 2
- 229940071870 hydroiodic acid Drugs 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 239000011973 solid acid Substances 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 238000010924 continuous production Methods 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000001728 nano-filtration Methods 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000002994 raw material Substances 0.000 description 9
- 239000004593 Epoxy Substances 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 8
- 238000003860 storage Methods 0.000 description 8
- 238000005903 acid hydrolysis reaction Methods 0.000 description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- 238000001514 detection method Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 125000002091 cationic group Chemical group 0.000 description 4
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 229920000609 methyl cellulose Polymers 0.000 description 4
- 239000001923 methylcellulose Substances 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000006683 Mannich reaction Methods 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- XENVCRGQTABGKY-ZHACJKMWSA-N chlorohydrin Chemical compound CC#CC#CC#CC#C\C=C\C(Cl)CO XENVCRGQTABGKY-ZHACJKMWSA-N 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
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- 239000002244 precipitate Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
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- 238000000921 elemental analysis Methods 0.000 description 2
- 230000001804 emulsifying effect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000005311 nuclear magnetism Effects 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 1
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- 150000003973 alkyl amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000010364 biochemical engineering Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
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- 150000001875 compounds Chemical class 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
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- 239000010419 fine particle Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 150000002462 imidazolines Chemical class 0.000 description 1
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- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10C—WORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
- C10C3/00—Working-up pitch, asphalt, bitumen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2395/00—Bituminous materials, e.g. asphalt, tar or pitch
Abstract
The invention discloses aminated lignin and a preparation method and application thereof. The preparation method comprises the following steps: (1) respectively and simultaneously pumping an epoxy chloropropane aqueous solution and an amination reagent aqueous solution into a first micro mixer in a microchannel reaction device, mixing, and then introducing into a first microreactor in the microchannel reaction device; (2) and (2) simultaneously pumping the alkali solution of the degraded lignin and the effluent liquid of the first microreactor into a second mixer in the microreactor while performing the step (1), mixing, introducing the mixture into a second microreactor in the microreactor, and collecting the effluent liquid of the second microreactor to obtain the lignin-degrading catalyst. The invention has the following advantages: (1) after pretreatment, the molecular weight is reduced, the content of phenolic hydroxyl is increased, and the reactive sites are increased. (2) The preparation process of the invention not only can realize continuous production, but also can shorten amination reaction time, has low energy consumption and improves production efficiency.
Description
Technical Field
The invention belongs to the technical field of biochemical engineering, and particularly relates to aminated lignin and an application of a preparation method thereof in an asphalt emulsifier.
Background
Fossil resources such as coal, oil, natural gas and the like on the earth belong to non-renewable resources and are main energy sources in human life and national industrial development. Along with the resource crisis and the increasing awareness of human beings to the environment, the development of alternative resources is imminent, and lignin is a natural polymer with a complex structure, is second to cellulose in abundance in nature, and belongs to an effective renewable resource.
Asphalt is generally used in the form of hot asphalt, cutback asphalt, and emulsified asphalt, in which viscous asphalt is heated to a fluid state, dispersed in an aqueous solution containing an emulsifier in the form of fine particles by the action of mechanical shear, and formed into a stable oil-in-water type asphalt emulsion. The emulsified asphalt can be used at normal temperature, the emulsified asphalt is developed through anionic and cationic processes, and the current cationic emulsifiers for asphalt comprise alkyl amines, amido amines, quaternary ammonium salts, imidazolines, lignins and the like. Compared with the anionic emulsified asphalt, the emulsified asphalt prepared by the cationic emulsifier has the advantages of slow demulsification time, strong adhesiveness and good stability, and can shorten the surface forming time.
The amination modification of lignin, mainly using lignin extracted from papermaking black liquor as raw material, and using Mannich reaction or epoxy amination reaction to make lignin undergo the process of amination modification so as to synthesize cationic lignin amine. Because the active sites of lignin are less and the competitive steric hindrance of phenolic hydroxyl groups causes poorer Mannich reaction grafting efficiency, the epoxy lignin prepared by the traditional epoxy amination reaction is grafted with the aminated product firstly, and the epoxy lignin is difficult to be applied to a continuous production system due to the difference of the solubility of the epoxy lignin. Therefore, it is desirable to construct a system that can continuously produce aminated lignin.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to solve the technical problems of low reaction speed, high crosslinking degree, low amine grafting rate, high energy consumption, low production efficiency, difficulty in realizing continuous production, complex post-treatment, long time period and the like in the synthesis process of lignin amination in the prior art, and provides aminated lignin and a preparation method thereof.
The technical problem to be solved by the invention also comprises the application of the aminated lignin prepared by the method in emulsified asphalt.
In order to solve the technical problem, the invention discloses a preparation method of aminated lignin, which comprises the following steps:
(1) respectively and simultaneously pumping an epoxy chloropropane aqueous solution and an amination reagent aqueous solution into a first micro mixer in a micro-channel reaction device, mixing, and then introducing into a first microreactor in the micro-reaction device to prepare a chlorohydrin intermediate;
(2) and (2) simultaneously pumping the alkali solution of the degraded lignin and the effluent liquid of the first microreactor into a second mixer in the microreactor while performing the step (1), mixing, introducing the mixture into a second microreactor in the microreactor, and collecting the effluent liquid of the second microreactor to obtain the aminated lignin solution.
In the step (1), the concentration of the epichlorohydrin in the epichlorohydrin aqueous solution is 0.2-6 mol/L; the amination reagent is an aliphatic amine compound; preferably diethylamine, dimethylamine, triethylene diamine, triethylamine; the concentration of the amination reagent in the amination reagent aqueous solution is 0.2-6 mol/L; the flow ratio of the epoxy chloropropane aqueous solution pumped into the first micro mixer in the microchannel reaction device to the flow ratio of the amination reagent aqueous solution pumped into the first micro mixer in the microchannel reaction device is 1: 0.5-1: 2, preferably 1: 1; in the first microreactor, the reaction temperature is 25-70 ℃, and the reaction residence time is 2-20 min; wherein the reaction temperature is preferably 60 to 70 ℃, and more preferably 70 ℃.
In the step (2), the degraded lignin can effectively increase oxygen-containing active structural units such as phenolic hydroxyl, alcoholic hydroxyl and the like.
In the step (2), the preparation method of the degraded lignin is to perform acidolysis reaction on the lignin and an acidolysis catalyst in a solvent; wherein, the acidolysis catalyst is any one or the combination of two of hydrobromic acid and hydroiodic acid; the solvent is any one or the combination of two of N, N-dimethylformamide and tetrahydrofuran; the mass volume ratio of the lignin to the solvent is 0.2-0.5 g/mL; the mass ratio of the acidolysis catalyst to the lignin is (0.05-2): 1; the reaction temperature is 70-110 ℃, and the reaction time is 1-3 h. Wherein the heating mode is microwave heating.
In the step (2), the preparation method of the degraded lignin is to pyrolyze the lignin at 140-200 ℃ for 1-3 h. Wherein the heating mode is microwave heating.
In the step (2), the preparation method of the degraded lignin comprises the steps of putting the lignin into a solvent, adding a catalyst, and carrying out high-pressure hydrogenolysis reaction; wherein, the solvent is any one or the combination of two of methanol and ethanol; the catalyst is a hydrogenation metal loaded solid acid catalyst; the mass-volume ratio of the lignin to the solvent is 20-80 mg/mL; the mass ratio of the lignin to the catalyst is 1 (0.02-0.05), and the high-pressure reaction is carried out for 6-12 hours at the hydrogen pressure of 2-6 MPa and the temperature of 160-250 ℃.
In the step (2), the concentration of the degraded lignin in the alkali solution of the degraded lignin is 100-200 g/L; the alkali solution is 0.3-0.5 mol/L sodium hydroxide aqueous solution.
In the step (2), the flow ratio of the flow of the alkali solution of the degraded lignin pumped into the second micro mixer in the microchannel reaction device to the flow of the material at the outlet of the first microreactor is 1: 0.5-1: 2, preferably 1: 1; in the second microreactor, the reaction temperature is 25-70 ℃ (preferably 40 ℃), and the reaction residence time is 2-20 min (preferably 5 min).
And (3) after the reaction in the step (2) is finished, carrying out nanofiltration desalination concentration on the aminated lignin solution to obtain a concentrated solution with a certain concentration. Wherein the nanofiltration is performed by adopting a nanofiltration membrane with the molecular weight cutoff of 200-500 Da to obtain a concentrated solution which does not penetrate through the filtration membrane; the pH value of the nanofiltration end point concentrated solution is 4-8, and the concentration of the concentrated solution after nanofiltration is 2-20 g/L.
Wherein, the microchannel reaction device comprises a first feeding pump, a second feeding pump, a third feeding pump, a first micromixer, a second micromixer, a first microreactor, a second microreactor and a receiver; the first feeding pump and the second feeding pump are connected to a first micro mixer in a parallel mode through pipelines, the first micro mixer is connected with the first microreactor in series, a discharge port of the first microreactor and the third feeding pump are connected to a second micro mixer in a parallel mode, the second micro mixer is sequentially connected with the second microreactor and a receiver in series, and the first feeding pump and the second feeding pump are connected through pipelines.
The microchannel reaction device has the advantages of short intermolecular diffusion distance, large specific surface area of the microchannel, high mass transfer and heat transfer speeds and the like, and can realize higher reaction rate. Meanwhile, in the reaction process, the whole process is mobile, so that the agglomeration of the compounds is reduced to a great extent, and the product yield is increased.
The application of the aminated lignin prepared by the method in the emulsified asphalt is also within the protection scope of the invention.
The application comprises the steps of concentrating the prepared aminated lignin solution to 15-25 g/L (preferably 20g/L), preheating to 40-50 ℃, preheating asphalt to 120-140 ℃, and then mixing the preheated aminated lignin solution, the preheated asphalt and the stabilizer according to a ratio of 90-120 mL: 90-120 g: adding the mixture into an asphalt emulsifier for emulsification at a dosage ratio of 0.15-0.3 mmol, and obtaining emulsified asphalt at an outlet. Wherein the stabilizer is methylcellulose, grease and the like, preferably methylcellulose; the asphalt emulsifying machine is a rubber mill or a continuous emulsifying machine.
Has the advantages that: compared with the prior art, the invention has the following advantages:
(1) after the technology provided by the invention is pretreated, the molecular weight is reduced, the content of phenolic hydroxyl is increased, and the active sites of the epoxy amination reaction can be increased.
(2) The microchannel reactor has the advantages of short amination reaction time, less amination reagent consumption, low energy consumption, high amination grafting rate, continuous production and high production efficiency, and is suitable for industrial production.
(3) And a nanofiltration post-treatment mode is adopted, so that other impurities are not introduced, and the post-treatment efficiency is improved.
(4) The mass transfer effect of the micro-reaction is good in the reaction process, and the selectivity and the nitrogen content of the reaction are superior to those of the prior preparation method.
(5) Compared with the prior art that the epoxy amination reaction is firstly prepared into the epoxy lignin and then the grafted amination product can not be continuously produced, the preparation process of the invention not only can be used for continuously producing, but also can shorten the amination reaction time, has low energy consumption and improves the production efficiency; in addition, the mass transfer effect of the micro-reaction in the reaction process is good, and the selectivity and the nitrogen content of the reaction are superior to those of the prior preparation method.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of a pretreated with an acid hydrolysis.
FIG. 2 is a schematic view of a microchannel reactor apparatus.
FIG. 3 is a nuclear magnetic map of aminated lignin.
FIG. 4 is a scheme of this reaction.
Detailed Description
The invention will be better understood from the following examples. However, those skilled in the art will readily appreciate that the description of the embodiments is only for illustrating the present invention and should not be taken as limiting the invention as detailed in the claims.
In the present invention, as shown in fig. 2, the microchannel reaction apparatus comprises a first feeding pump, a second feeding pump, a third feeding pump, a first micromixer, a second micromixer, a first microreactor, a second microreactor, and a receiver; the first feeding pump and the second feeding pump are connected to a first micro mixer in a parallel mode through pipelines, the first micro mixer is connected with the first microreactor in series, a discharge port of the first microreactor and the third feeding pump are connected to a second micro mixer in a parallel mode, the second micro mixer is sequentially connected with the second microreactor and a receiver in series, and the first feeding pump and the second feeding pump are connected through pipelines.
The micromixer is slitplatamixerlh 25 (HastelloyC); purchased from Ehrfeld MikrotechnikBTS GmbH, model 0109-4-0004-F.
The microreactor is a meander reactivor HC, a sandwich reactivor HC and a fixdbed meander reactivor HC; preferably sandwich reactivor HC, available from Ehrfeld MikrotechnikBTSGmbH, having models 0211-2-0314-F, respectively; 0222-2-2004-F.
The tubular temperature control module is available from Ehrfeld MikrotechnikBTSGmbH, model 0501-2-1004-F.
The inner diameter of the tube for the micro-reaction was 0.25cm, and the volume of the tube was 100 mL.
Example 1: degradation-acidolysis of lignin
5g of lignin dissolved in 20mL of DMF was added to a 50mL reaction flask, and 5g of 10% HBr was added thereto, followed by reaction at 90 ℃ for 30min in a microwave reactor. After the reaction is finished, cooling the reactant to room temperature, dropwise adding the reactant into 200mL of hydrochloric acid solution with the mass fraction of 2%, stirring for 30min, centrifuging, taking the precipitate, washing the precipitate with distilled water, washing the supernatant to be neutral, and freeze-drying, wherein the nuclear magnetic hydrogen spectrum of the precipitate is shown in figure 1; detecting changes of molecular weight and hydroxyl group before and after acidolysis by nuclear magnetism and GPC[1]The results are shown in the following table:
TABLE 1 changes in molecular weight and phenolic hydroxyl groups before and after acid hydrolysis of lignin
Examples 2 to 5: preparation of chlorohydrin intermediates
Preparing an aqueous solution of epichlorohydrin in a first raw material storage tank, wherein the concentration of the epichlorohydrin is3mol/L, and an aqueous solution of an amination reagent diethylamine is arranged in the second raw material storage tank, wherein the concentration is 3 mol/L. Pumping a first raw material storage tank (epoxy chloropropane solution) and a second raw material storage tank (diethylamine aqueous solution) into a first micro mixer in a microchannel reaction device according to the volume flow ratio of 1:1, mixing, flowing into a first micro reactor, keeping for a period of time at a certain temperature, and detecting reaction liquid GC-MS (gas chromatography-mass spectrometry) discharged from a micro-structure reactor I[2]Then, carrying out quantitative detection, wherein the detection result is as follows:
ep2 epichlorohydrin and diethylamine after microchannel reaction chlorohydrin intermediate yield
Comparative examples 1 to 4:
preparing a raw lignin alkali solution in a third raw material storage tank, wherein the ratio of lignin to alkali sodium hydroxide to water is 100g to 120 g: 1L, pumping the flow rates of a third raw material storage tank (lignin alkali solution) and an outlet of a first micro-reactor (embodiment 5) into a second micro-mixer in a microchannel reaction device according to the volume flow ratio of 1:1, mixing, flowing into the second micro-reactor, keeping for a period of time at a certain temperature, performing nanofiltration and spray drying on reaction liquid from the micro second micro-reactor by using a nanofiltration membrane with the molecular weight cutoff of 200-500 Da, and performing element analysis and detection, wherein the reaction route is shown in figure 4, and the detection result is as follows:
TABLE 2 Nitrogen content of original lignin after micro-channel reaction amination
Examples 6 to 17
An acid hydrolysis lignin alkali solution (prepared in example 1) is prepared in a third raw material storage tank, and the ratio of the acid hydrolysis lignin to the (0.3mol/L) sodium hydroxide solution is 100g: 1L, pumping the flow rates of a third raw material storage tank (acid hydrolysis lignin alkali solution) and an outlet of a first microreactor (example 5) into a microstructure reactor II according to the volume flow ratio of 1:1, and carrying out reaction at a certain temperatureKeeping for a period of time, performing nanofiltration and spray drying on reaction liquid from the second microreactor by adopting a nanofiltration membrane with the molecular weight cutoff of 200-500 Da, and then performing elemental analysis and nuclear magnetism1H NMR (FIG. 3) was measured, and the results of elemental analysis were as follows:
TABLE 3 acid hydrolysis of lignin by microchannel reaction and amination of lignin nitrogen content
Example 18: hydrogenolysis of
1.5g of lignin was dissolved in 20mL of methanol in a 50mL reaction flask, 0.1g of (Pd) catalyst was added, and the mixed solution was charged into a 100mL autoclave, and 2MPa of hydrogen was introduced to the autoclave to react at 160 ℃ for 6 hours. After the reaction is finished, cooling the reactant to room temperature, filtering, and then carrying out rotary evaporation drying on the filtrate to obtain a sample. The changes in molecular weight and phenolic hydroxyl group content before and after hydrogenolysis were measured by GPC, and the results are shown in Table 1 below.
Example 19: pyrolysis
1.5g of lignin is pyrolyzed at 200 ℃ for 3h to obtain pyrolyzed lignin. Changes in molecular weight and phenolic hydroxyl group content before and after pyrolysis were measured by GPC, and the results are shown in table 1 below.
TABLE 1 changes in molecular weight and phenolic hydroxyl groups before and after acid hydrolysis of lignin
| Sample (I) | Phenolic hydroxyl group content (wt%) | Molecular weight (Da) |
| Hydrogenolysis of lignin | 4.24 | 2127 |
| Pyrolyzed lignin | 4.23 | 2239 |
Example 20: preparation of emulsified asphalt
And (3) performing nanofiltration on the aminated lignin solution obtained by the second microreactor in the examples 17-19 through a nanofiltration machine. Removing residual sodium hydroxide and amination reagent, determining nanofiltration end point when the pH of the concentrated solution is tested to be 8.0, simultaneously checking the solid content of the concentrated solution, and adding water until the concentration of aminated lignin is 20 g/L.
Heating the aminated lignin solution to 40 ℃, heating asphalt to 130 ℃, and mixing the aminated lignin solution, asphalt and methylcellulose according to the weight ratio of 100mL (20 g/L): 100g: 0.1g (0.22mmol) of the emulsified asphalt is added into an RH-5 rubber mill for emulsification, and the outlet of the emulsified asphalt is the emulsified asphalt which is found to be fast-cracking type by the detection of T0658-.
Comparative example 5
In the same way as in example 20, aminated lignin was replaced by non-aminated lignin.
Heating the non-aminated lignin solution to 40 ℃, heating the asphalt to 130 ℃, and mixing the aminated lignin solution, asphalt and methylcellulose according to the weight ratio of 100mL (20 g/L): 100g: 0.1g (0.22mmol) was added to the mill and emulsified, and the bitumen was not successfully emulsified at the outlet.
Therefore, the method improves the active sites through degradation, increases the nitrogen content of aminated lignin, and prepares the lignin cationic surfactant, so that the emulsified asphalt can be effectively prepared.
The invention provides a thought and a method for applying aminated lignin and a preparation method thereof in asphalt emulsifier, and a method and a way for realizing the technical scheme are many, the above description is only a preferred embodiment of the invention, and it should be noted that for a person skilled in the art, a plurality of improvements and decorations can be made without departing from the principle of the invention, and the improvements and decorations are also regarded as the protection scope of the invention. All the components not specified in the present embodiment can be realized by the prior art.
Reference documents:
[1] preparation and application of zhangwei, biological refining lignin-based phenolic resin [ D ]. beijing: china forestry science research institute, 2013: 1-167.
[2]Du,X.；Li,J.；
M.E.,Modification of industrial softwoodkraft lignin using Mannich reaction with and without phenolationpretreatment.Industrial Crops and Products2014,52,729-735.
Claims (10)
1. The preparation method of aminated lignin is characterized by comprising the following steps:
(1) respectively and simultaneously pumping an epoxy chloropropane aqueous solution and an amination reagent aqueous solution into a first micro mixer in a microchannel reaction device, mixing, and then introducing into a first microreactor in the microchannel reaction device;
(2) and (2) simultaneously pumping the alkali solution of the degraded lignin and the effluent liquid of the first microreactor into a second mixer in the microreactor while performing the step (1), mixing, introducing the mixture into a second microreactor in the microreactor, and collecting the effluent liquid of the second microreactor to obtain the aminated lignin solution.
2. The preparation method according to claim 1, wherein in the step (1), the concentration of the epichlorohydrin in the aqueous solution is 0.2-6 mol/L; the amination reagent is an aliphatic amine compound; the concentration of the amination reagent in the amination reagent aqueous solution is 0.2-6 mol/L; the flow ratio of the epoxy chloropropane aqueous solution pumped into the first micro mixer in the microchannel reaction device to the flow ratio of the amination reagent aqueous solution pumped into the first micro mixer in the microchannel reaction device is 1: 0.5-1: 2; in the first microreactor, the reaction temperature is 25-70 ℃, and the reaction residence time is 2-20 min.
3. The method according to claim 1, wherein in the step (2), the degraded lignin is prepared by subjecting lignin and an acidolysis catalyst to an acidolysis reaction in a solvent;
wherein, the acidolysis catalyst is any one or the combination of two of hydrobromic acid and hydroiodic acid; the solvent is any one or the combination of two of N, N-dimethylformamide and tetrahydrofuran; the mass volume ratio of the lignin to the solvent is 0.2-0.5 g/mL; the mass ratio of the acidolysis catalyst to the lignin is (0.05-2): 1; the reaction temperature is 70-110 ℃, and the reaction time is 1-3 h.
4. The preparation method according to claim 1, wherein in the step (2), the degraded lignin is prepared by pyrolyzing lignin at 140-200 ℃ for 1-3 h.
5. The preparation method according to claim 1, wherein in the step (2), the degraded lignin is prepared by placing the lignin in a solvent, adding a catalyst, and performing a high-pressure hydrogenolysis reaction;
wherein, the solvent is any one or the combination of two of methanol and ethanol; the catalyst is a hydrogenation metal loaded solid acid catalyst; the mass-volume ratio of the lignin to the solvent is 20-80 mg/mL; the mass ratio of the lignin to the catalyst is 1 (0.02-0.05), and the high-pressure reaction is carried out for 6-12 hours at the hydrogen pressure of 2-6 MPa and the temperature of 160-250 ℃.
6. The preparation method according to claim 1, wherein in the step (2), the concentration of the degraded lignin in the alkali solution of the degraded lignin is 100-200 g/L; the alkali solution is 0.3-0.5 mol/L sodium hydroxide aqueous solution.
7. The preparation method according to claim 1, wherein in the step (2), the flow rate of the alkali solution of the degraded lignin pumped into the second micro mixer in the microchannel reaction device to the flow rate of the first microreactor outlet material is 1: 0.5-1: 2; in the second micro-reactor, the reaction temperature is 25-70 ℃, and the reaction residence time is 2-20 min.
8. The process of claim 1 wherein the microchannel reactor apparatus comprises a first feed pump, a second feed pump, a third feed pump, a first micromixer, a second micromixer, a first microreactor, a second microreactor, and a receiver; the first feeding pump and the second feeding pump are connected to a first micro mixer in a parallel mode through pipelines, the first micro mixer is connected with the first microreactor in series, a discharge port of the first microreactor and the third feeding pump are connected to a second micro mixer in a parallel mode, the second micro mixer is sequentially connected with the second microreactor and a receiver in series, and the first feeding pump and the second feeding pump are connected through pipelines.
9. Use of aminated lignin prepared by the method of any one of claims 1 to 8 in emulsified asphalt.
10. The application of claim 9, wherein the aminated lignin solution prepared by the method in claim 1 is concentrated to 15-25 g/L, preheated to 40-50 ℃, asphalt is preheated to 120-140 ℃, and then the preheated aminated lignin solution, the preheated asphalt and the stabilizer are mixed according to the ratio of 90-120 mL: 90-120 g: adding the mixture into an asphalt emulsifier for emulsification at a dosage ratio of 0.15-0.3 mmol, and obtaining emulsified asphalt at an outlet.
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| CN115707685A (en) * | 2021-08-20 | 2023-02-21 | 中国石油化工股份有限公司 | Method, product and system for preparing amine-epihalohydrin polymerized monomer |
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