CN102746516A - Lignin asphalt emulsifier with high temperature tolerance, its preparation method and application - Google Patents
Lignin asphalt emulsifier with high temperature tolerance, its preparation method and application Download PDFInfo
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- CN102746516A CN102746516A CN2012101988796A CN201210198879A CN102746516A CN 102746516 A CN102746516 A CN 102746516A CN 2012101988796 A CN2012101988796 A CN 2012101988796A CN 201210198879 A CN201210198879 A CN 201210198879A CN 102746516 A CN102746516 A CN 102746516A
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- high temperature
- temperature tolerance
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- 239000010426 asphalt Substances 0.000 title claims abstract description 76
- 239000003995 emulsifying agent Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 229920005610 lignin Polymers 0.000 title abstract description 14
- 150000001412 amines Chemical class 0.000 claims abstract description 22
- 150000001875 compounds Chemical class 0.000 claims abstract description 15
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 14
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims abstract 9
- 229920000768 polyamine Polymers 0.000 claims abstract 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 54
- 238000006243 chemical reaction Methods 0.000 claims description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 239000012670 alkaline solution Substances 0.000 claims description 12
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- IMUDHTPIFIBORV-UHFFFAOYSA-N aminoethylpiperazine Chemical compound NCCN1CCNCC1 IMUDHTPIFIBORV-UHFFFAOYSA-N 0.000 claims description 5
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical group OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 150000002978 peroxides Chemical class 0.000 claims description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 238000004945 emulsification Methods 0.000 abstract description 2
- 239000007800 oxidant agent Substances 0.000 abstract 2
- 239000003513 alkali Substances 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 56
- 239000000243 solution Substances 0.000 description 28
- 238000003756 stirring Methods 0.000 description 21
- 238000005303 weighing Methods 0.000 description 21
- -1 polyoxyethylene nonylphenol Polymers 0.000 description 17
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 15
- 238000011156 evaluation Methods 0.000 description 14
- 239000007788 liquid Substances 0.000 description 13
- 239000004570 mortar (masonry) Substances 0.000 description 13
- 238000004811 liquid chromatography Methods 0.000 description 9
- 239000000839 emulsion Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 150000001299 aldehydes Chemical class 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- 239000003638 chemical reducing agent Substances 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 238000012545 processing Methods 0.000 description 7
- 239000000344 soap Substances 0.000 description 7
- 239000012874 anionic emulsifier Substances 0.000 description 6
- 150000001734 carboxylic acid salts Chemical class 0.000 description 6
- 239000000470 constituent Substances 0.000 description 6
- 230000001804 emulsifying effect Effects 0.000 description 6
- 239000012266 salt solution Substances 0.000 description 6
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000008293 association colloid Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000003550 marker Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229960001124 trientine Drugs 0.000 description 1
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
Abstract
The invention discloses a lignin asphalt emulsifier with high temperature tolerance, its preparation method and application. The emulsifier is prepared by the following steps: reacting amine, solvent and aldehyde for 1-3 h at 10-30 DEG C, wherein each mole of amine needs 0-50ml of solvent, and the molar ratio of amine to aldehyde is 1:1-1:5; adding a metal ion compound and an oxidizing agent into an alkali lignin solution having the mass concentration of 25-40% and Ph value of 8-11, and reacting for 1-5 h at 60-100 DEG C, wherein the dosing quantity of the metal ion compound is 0.1-0.5 % of the weight of lignin, the dosing quantity of the oxidizing agent is 3.5-10 % of the weight of lignin, and each 0.1 mole of polyamine needs 25-40g of lignin; and mixing the products of the above steps to react for 3-7 h at 30-70 DEG C. The emulsifier disclosed herein has good emulsification performance and good temperature tolerance.
Description
Technical field
The present invention relates to a kind of high temperature tolerance xylogen asphalt emulsifier, its preparation method and application thereof, and the emulsified bitumen that comprises high temperature tolerance xylogen asphalt emulsifier of the present invention.
Background technology
Current China papermaking wastewater is direct discharging mostly, and contained xylogen is a kind of broad-spectrum chemical feedstocks in the papermaking wastewater.China's paper-making effluent quantity discharged is about 5,000,000,000 tons, occupies the first place of China's all types of industries quantity discharged, and paper industry is the most serious to the pollution of water surrounding.The asphalt emulsifier that is applicable to the CA mortar at present is mainly lignin; Therefore; The xylogen that adopts paper industry to produce prepares CA mortar special asphalt emulsifying agent, can economize on resources, protect environment, to promoting China's energy-saving and emission-reduction implementation significant.
Because residing position of CA mortar and construction technology have determined it must have good flowability; And emulsified bitumen is a kind of thermodynamic unstable system; And there is very intensive interaction between the cement in the CA mortar, causes CA mortar flowability to lose greatly, temperature sensitive, operable time are lacked.And will address the above problem, must start with from emulsifying agent.Although Japan and Germany have carried out a large amount of work in this respect, but still can only in 5～35 ℃ of temperature scopes, construct, this has brought very big difficulty for the hot weather construction of CA mortar.
Summary of the invention
The purpose of this invention is to provide a kind of high temperature tolerance xylogen asphalt emulsifier, its preparation method and application thereof, and the emulsified bitumen that comprises high emulsibility ability xylogen asphalt emulsifier of the present invention.
To achieve these goals, technical scheme of the present invention is:
A kind of high temperature tolerance xylogen of the present invention asphalt emulsifier makes as follows:
A, with amine, solvent and aldehyde under 10 ° of C～30 ° C, reaction 1～3h, wherein, every mole of amine needs the 0-50ml solvent, the mol ratio of amine and aldehyde is 1:1～1:5;
B, be that 25-40%, Ph add metal ion compound and oxygenant in the xylogen alkaline solution of 8-11 with mass concentration; Under 60 ° of C～100 ° C; Reaction 1～5h, wherein, the quality consumption of metal ion compound is the 1-5 ‰ of xylogen quality; The quality consumption of oxygenant is the 3.5-10% of xylogen quality, and wherein per 0.1 mole of amine needs the 25-40g xylogen;
C, will go up steps A and step B products therefrom is blended under 30 ° of C～70 ° C, reaction 3-7h;
Above-mentioned amine is diethylolamine, aminoethyl piperazine, piperazine or NH
2(CH
2CH
2NH)
nThe mixture of any proportioning of one or more among the H, wherein n is not more than 6 integer; Aldehyde does
R
1Alkyl or aromatic base for H, no α H; Solvent is methyl alcohol, ethanol or water.
Xylogen of the present invention available from Jiangxi, ground such as the real dimension of Fujian, virtue dimension gram, Wanyuan, the xylogen that adopts the wood pulp acid-precipitation method to prepare is configured to the xylogen alkaline solution of different concns, different Ph values in use as required.
In order to make the gained emulsifying agent that better emulsifying effectiveness can be arranged, practice thrift cost simultaneously, above-mentioned oxygenant is preferably ydrogen peroxide 50, O
3, KClO
3, KMnO
4Or Na
2O
2In the mixture of one or more any proportionings.
In order to make the gained emulsifying agent that better emulsifying effectiveness can be arranged, practice thrift cost simultaneously, the above-mentioned metal ion compound of stating is preferably FeCl
3, FeSO
4, CuSO
4, MnO
2, ZnSO
4, ZnCl
2Or the mixture of one or more any proportionings among the KBr.Metal ion compound has catalytic effect to reaction.
In order to make the gained emulsifying agent that better emulsifying effectiveness can be arranged, R in the above-mentioned aldehyde
1Be preferably H, phenyl or butyl.
In order to make the gained emulsifying agent that better emulsifying effectiveness can be arranged, practice thrift cost simultaneously, the quality consumption of above-mentioned metal ion compound is preferably the 2-3 ‰ of xylogen quality.
The preparation method of above-mentioned a kind of high temperature tolerance xylogen asphalt emulsifier comprises the steps:
A, with amine, solvent and aldehyde under 10 ° of C～30 ° C, reaction 1～3h, wherein, every mole of amine needs the 0-50ml solvent, the mol ratio of amine and aldehyde is 1:1～1:5;
B, be that 25-40%, Ph add metal ion compound and oxygenant in the xylogen alkaline solution of 8-11 with mass concentration; Under 60 ° of C～100 ° C; Reaction 1～5h, wherein, the quality consumption of metal ion compound is the 1-5 ‰ of xylogen quality; The quality consumption of oxygenant is the 3.5-10% of xylogen quality, and wherein per 0.1 mole of amine needs the 25-40g xylogen;
C, will go up steps A and step B products therefrom is blended under 30 ° of C～70 ° C, reaction 3-7h;
Above-mentioned amine is diethylolamine, aminoethyl piperazine, piperazine or NH
2(CH
2CH
2NH)
nThe mixture of any proportioning of one or more among the H, wherein n is not more than 6 natural number; Aldehyde does
R
1Alkyl or aromatic base for H, no α H; Solvent is methyl alcohol, ethanol or water.
When high temperature tolerance xylogen asphalt emulsifier of the present invention uses, when its consumption is the 2-6% of emulsified bitumen quality, can reach good emulsifying effectiveness.
Gained emulsifying agent of the present invention and polyoxyethylene nonylphenol be composite to have better emulsifying effectiveness, not only emulsification easily, and good heat resistance is arranged.
Embodiment
In order to understand the present invention better, further illustrate content of the present invention below in conjunction with embodiment, but content of the present invention not only is confined to following embodiment.
In following examples, transformation efficiency calculates through liquid chromatography.The condition of liquid chromatography separated product is: adopt the reverse chromatograms post, moving phase is methanol=85/15, and the uv-absorbing wavelength is chosen in 237nm.Adopt marker method to survey transformation efficiency.
The flow cone time tests according to " the provisional technological bar of the plate type unballasted track cement emulsified pitch of passenger dedicated railway line CRTS II type ".
Embodiment 1
40% Jiangxi xylogen (Jiangxi Province Huanggang mountain xylogen development department) alkaline solution 100g with PH=10.5 is warmed up to 60 ° of C, and 7.8% 30% concentration ydrogen peroxide 50 and the mass content that drips active constituent content and be the xylogen quality is 1 ‰ FeCl of xylogen quality
3After, be warmed up to 90 ° of C reaction 4h and obtain the xylogen carboxylate salt; The 0.1mol diethylolamine is dissolved in the ethanol of 25ml, the phenyl aldehyde that under 10 ° of C, drips 0.5mol is in above-mentioned solution, and reaction 2h obtains intermediate A solution under 10 ° of C; Secondly middle A drips of solution is added in the xylogen carboxylate salt, elevated temperature to 60 ° C reacts 5h and obtains the xylogen anionic asphalt emulsion then.It is 71.3% that product records the lignin conversion rate through liquid chromatography, and thick liquid stays does the experiment of preparation emulsified bitumen.
Take by weighing 4g polyoxyethylene nonylphenol (EO=40 earlier; Producer: the AR of Shanghai Heng Ji chemical industry International Trading Company Ltd), add 55 ° of C warm water 100g and make its solution, again to wherein adding the above-mentioned self-control xylogen of 38g emulsifying agent; Water is to 350g then, drips 30% NaOH (commercially available) to the PH=11.Add water to 400g at last, give over to emulsified bitumen.
Take by weighing 38g LA (producer: the real dimension gram of virtue dimension, this xylogen emulsifying agent are effect Compositional type emulsifying agent preferably in the prior art) xylogen emulsifying agent earlier, water is to 350g then, drips 30% NaOH (commercially available) to the PH=11.Add water to 400g at last, give over to emulsified bitumen.
Get SK70# pitch (Jiangyin Golden Leaf Products Co., Ltd) 600g, be heated to 140 ° of C.Above-mentioned soap lye 400g is heated to 60 ° of C, through colloidal mill (model: DSH100 processing parameter: mill spacing 0.015mm, rotating speed 2000r/min) preparation bitumen emulsion.Obtain even, fine and smooth negatively charged ion and split slow-setting emulsified asphalt slowly.
The preparation of CA mortar: siccative (Jiangsu Botexin Materials Co., Ltd) the preheating 24h under 50 ° of C that gets 2000g.Add emulsified bitumen 320g in the restir pot.Take by weighing DF201 type skimmer (Jiangsu Botexin Materials Co., Ltd) 0.15g, PCA-RX water reducer (Jiangsu Botexin Materials Co., Ltd) 3.5g adds water to 185g.The above-mentioned aqueous solution is joined respectively in the emulsified bitumen pot stirring at a slow speed under the 2min (60r/min) with gathering materials, stirs 3min (200r/min) fast, after stir 2min (60r/min) at a slow speed, survey 0min, 30min, 1h, 2h, 3h, 4h, flow cone time.Need in the thermostat container of 50 ° of C, to be incubated after each the measurement.Table 1 is the performance evaluation table of emulsifying agent.
The performance evaluation of table 1 emulsifying agent
Embodiment 2
The real dimension gram of 40% virtue dimension xylogen alkaline solution 100g (virtue is tieed up real Virbac) with PH=9.5 is warmed up to 60 ° of C, adds effective constituent and be 3.5% O of xylogen quality
3With mass content be 1 ‰ FeSO of xylogen quality
4After, be warmed up to 30 ° of C reaction 1h and obtain the xylogen carboxylate salt; 0.1mol diethylenetriamine is dissolved into the ethanol liquid of 25ml, the formaldehyde that under 30 ° of C, drips 0.2mol is in above-mentioned solution, and reaction 3h obtains intermediate A solution under 30 ° of C; Secondly middle A drips of solution is added among the xylogen carboxylic acid salt solution, temperature is to 70 ° of C then, and reaction 5h obtains the xylogen anionic emulsifier.Recording the lignin conversion rate through liquid chromatography is 83.4%, and thick liquid stays does the experiment of preparation emulsified bitumen.
Take by weighing 4g polyoxyethylene nonylphenol (EO=40 earlier; Producer: the g AR of Shanghai Heng Ji chemical industry International Trading Company Ltd) adds 55 ° of C warm water 100g and makes its solution, again to wherein adding the above-mentioned self-control xylogen of 25g emulsifying agent; Water is to 350g then, drips 30% NaOH (commercially available) to the PH=11.Add water to 400g at last, give over to emulsified bitumen.
(producer: the xylogen emulsifying agent real dimension gram of virtue dimension), water is to 350g then, drips 30% NaOH (commercially available) to the PH=11 to take by weighing 25g LA earlier.Add water to 400g at last, give over to emulsified bitumen.
Get SK70# pitch (Jiangyin Golden Leaf Products Co., Ltd) 600g, be heated to 140 ° of C.Above-mentioned soap lye 400g is heated to 60 ° of C, through colloidal mill (model: DSH100 processing parameter: mill spacing 0.015mm, rotating speed 2000r/min) preparation bitumen emulsion.Obtain even, fine and smooth negatively charged ion and split slow-setting emulsified asphalt slowly.
The preparation of CA mortar: siccative (Jiangsu Botexin Materials Co., Ltd) the preheating 24h under 50 ° of C that gets 2000g.Add emulsified bitumen 320g in the restir pot.Take by weighing DF201 type skimmer (Jiangsu Botexin Materials Co., Ltd) 0.15g, PCA-RX water reducer (Jiangsu Botexin Materials Co., Ltd) 3.5g adds water to 185g.The above-mentioned aqueous solution is joined respectively in the emulsified bitumen pot stirring at a slow speed under the 2min (60r/min) with gathering materials, stirs 3min (200r/min) fast, after stir 2min (60r/min) at a slow speed, survey 0min, 30min, 1h, 2h, 3h, 4h, flow cone time.Need in the thermostat container of 50 ° of C, to be incubated after each the measurement.Table 2 is the performance evaluation table of emulsifying agent.
The performance evaluation of table 2 emulsifying agent
Embodiment 3
40% Fujian xylogen (Yongan association colloid Ltd) alkaline solution 100g with PH=10.5 is warmed up to 60 ° of C, adds effective constituent and be 3.5% KClO of xylogen quality
3With mass content be 3 ‰ CuSO of xylogen quality
4After, being warmed up to 100 ° of C, reaction 5h obtains the xylogen carboxylate salt; 0.1mol diethylenetriamine is dissolved into the ethanol liquid of 25ml, the uncle's butyraldehyde that under 20 ° of C, drips 0.4mol is in above-mentioned solution, and reaction 2.5h obtains intermediate A solution under 20 ° of C; Secondly middle A drips of solution is added among the xylogen carboxylic acid salt solution, elevated temperature to 35 ° C reacts 5h and obtains the xylogen anionic emulsifier then.Recording the lignin conversion rate through liquid chromatography is 57.8%, and thick liquid stays does the experiment of preparation emulsified bitumen.
Take by weighing 4g polyoxyethylene nonylphenol (EO=40 earlier; Producer: the g AR of Shanghai Heng Ji chemical industry International Trading Company Ltd) adds 55 ° of C warm water 100g and makes its solution, again to wherein adding the above-mentioned self-control xylogen of 30g emulsifying agent; Water is to 350g then, drips 30% NaOH (commercially available) to the PH=11.Add water to 400g at last, give over to emulsified bitumen.
Take by weighing earlier 30g LA (producer: the xylogen emulsifying agent real dimension gram of virtue dimension), add water to 350g then, drip 30% NaOH (commercially available) to the PH=11.Add water to 400g at last, give over to emulsified bitumen.
Get SK70# pitch (Jiangyin Golden Leaf Products Co., Ltd) 600g, be heated to 140 ° of C.Above-mentioned soap lye 400g is heated to 60 ° of C, through colloidal mill (model: DSH100 processing parameter: mill spacing 0.015mm, rotating speed 2000r/min) preparation bitumen emulsion.Obtain even, fine and smooth negatively charged ion and split slow-setting emulsified asphalt slowly.
The preparation of CA mortar: siccative (Jiangsu Botexin Materials Co., Ltd) the preheating 24h under 50 ° of C that gets 2000g.Add emulsified bitumen 320g in the restir pot.Take by weighing DF201 type skimmer (Jiangsu Botexin Materials Co., Ltd) 0.15g, PCA-RX water reducer (Jiangsu Botexin Materials Co., Ltd) 3.5g adds water to 185g.The above-mentioned aqueous solution is joined respectively in the emulsified bitumen pot stirring at a slow speed under the 2min (60r/min) with gathering materials, stirs 3min (200r/min) fast, after stir 2min (60r/min) at a slow speed, survey 0min, 30min, 1h, 2h, 3h, 4h, flow cone time.Need in the thermostat container of 50 ° of C, to be incubated after each the measurement.Table 3 is the performance evaluation table of emulsifying agent.
The performance evaluation of table 3 emulsifying agent
Embodiment 4
40% Wanyuan xylogen (Huaihua City Wanyuan auxiliary agent ltd) alkaline solution 100g with PH=10.5 is warmed up to 60 ° of C, adds effective constituent and be 10% Na of xylogen quality
2O
2With mass content be 2 ‰ MnO of xylogen quality
2After, being warmed up to 80 ° of C, reaction 3h obtains the xylogen carboxylate salt; 0.1mol triethylene tetramine is dissolved into the ethanol liquid of 25ml, the formaldehyde that under 20 ° of C, drips 0.2mol is in above-mentioned solution, and reaction 2h obtains intermediate A solution under 25 ° of C; Secondly middle A drips of solution is added among the xylogen carboxylic acid salt solution, elevated temperature to 55 ° C reacts 6h and obtains the xylogen anionic emulsifier then.Recording the lignin conversion rate through liquid chromatography is 91.4%, and thick liquid stays does the experiment of preparation emulsified bitumen.
Take by weighing 4g polyoxyethylene nonylphenol (EO=40 earlier; Producer: the g AR of Shanghai Heng Ji chemical industry International Trading Company Ltd); Add 55 ° of C warm water 100g and make its solution; To wherein adding the above-mentioned self-control xylogen of 35g emulsifying agent, add water to 350g then again, drip 30% NaOH (commercially available) to the PH=11.Add water to 400g at last, give over to emulsified bitumen.
Take by weighing earlier 35g LA (producer: the xylogen emulsifying agent real dimension gram of virtue dimension), add a certain amount of water then to 350g, drip 30% NaOH (commercially available) to the PH=11.Add water to 400g at last, give over to emulsified bitumen.
Get SK70# pitch (Jiangyin Golden Leaf Products Co., Ltd) 600g, be heated to 140 ° of C.Above-mentioned soap lye 400g is heated to 60 ° of C, through colloidal mill (model: DSH100 processing parameter: mill spacing 0.015mm, rotating speed 2000r/min) preparation bitumen emulsion.Obtain even, fine and smooth negatively charged ion and split slow-setting emulsified asphalt slowly.
The preparation of CA mortar: siccative (Jiangsu Botexin Materials Co., Ltd) the preheating 24h under 50 ° of C that gets 2000g.Add emulsified bitumen 320g in the restir pot.Take by weighing DF201 type skimmer (Jiangsu Botexin Materials Co., Ltd) 0.15g, PCA-RX water reducer (Jiangsu Botexin Materials Co., Ltd) 3.5g adds water to 185g.The above-mentioned aqueous solution is joined respectively in the emulsified bitumen pot stirring at a slow speed under the 2min (60r/min) with gathering materials, stirs 3min (200r/min) fast, after stir 2min (60r/min) at a slow speed, survey 0min, 30min, 1h, 2h, 3h, 4h, flow cone time.Need in the thermostat container of 50 ° of C, to be incubated after each the measurement.Table 4 is the performance evaluation table of emulsifying agent.
The performance evaluation of table 4 emulsifying agent
Embodiment 5
With 25% Jiangxi xylogen (Jiangxi Province Huanggang mountain xylogen development department) the alkaline solution 100g of H=10.5, elevated temperature to 60 ° C, the mass content that adds effective constituent is 7.0% acid KMnO of xylogen quality
4With mass content be 3 ‰ ZnSO of xylogen quality
4After, be warmed up to 75 ° of C reaction 3.5h and obtain the xylogen carboxylate salt; 0.1mol TEPA is dissolved into the ethanol liquid of 25ml, the formaldehyde that under 20 ° of C, drips 0.4mol is in above-mentioned solution, and reaction 1.5h obtains intermediate A solution under 20 ° of C; Secondly middle A drips of solution is added among the xylogen carboxylic acid salt solution, elevated temperature to 60 ° C reacts 3h and obtains the xylogen anionic emulsifier then.Recording the lignin conversion rate through liquid chromatography is 85.9%, and thick liquid stays does the experiment of preparation emulsified bitumen.
Take by weighing 4g polyoxyethylene nonylphenol (EO=40 earlier; Producer: the g AR of Shanghai Heng Ji chemical industry International Trading Company Ltd); Add 55 ° of C warm water 100g and make its solution; To wherein adding the above-mentioned self-control xylogen of 30g emulsifying agent, add water to 350g then again, drip 30% NaOH (commercially available) to the PH=11.Add water to 400g at last, give over to emulsified bitumen.
Take by weighing earlier 30g LA (producer: the xylogen emulsifying agent real dimension gram of virtue dimension), add water to 350g then, drip 30% NaOH (commercially available) to the PH=11.Add water to 400g at last, give over to emulsified bitumen.
Get SK70# pitch (Jiangyin Golden Leaf Products Co., Ltd) 600g, be heated to 140 ° of C.Above-mentioned soap lye 400g is heated to 60 ° of C, through colloidal mill (model: DSH100 processing parameter: mill spacing 0.015mm, rotating speed 2000r/min) preparation bitumen emulsion.Obtain even, fine and smooth negatively charged ion and split slow-setting emulsified asphalt slowly.
The preparation of CA mortar: siccative (Jiangsu Botexin Materials Co., Ltd) the preheating 24h under 50 ° of C that gets 2000g.Add emulsified bitumen 320g in the restir pot.Take by weighing DF201 type skimmer (Jiangsu Botexin Materials Co., Ltd) 0.15g, PCA-RX water reducer (Jiangsu Botexin Materials Co., Ltd) 3.5g adds water to 185g.The above-mentioned aqueous solution is joined respectively in the emulsified bitumen pot stirring at a slow speed under the 2min (60r/min) with gathering materials, stirs 3min (200r/min) fast, after stir 2min (60r/min) at a slow speed, survey 0min, 30min, 1h, 2h, 3h, 4h, flow cone time.Need in the thermostat container of 50 ° of C, to be incubated after each the measurement.Table 5 is the performance evaluation table of emulsifying agent.
The performance evaluation of table 5 emulsifying agent
Embodiment 6
With the real dimension gram of 40% virtue dimension xylogen (virtue is tieed up real Virbac) the alkaline solution 100g of PH=10.5, elevated temperature to 65 ° C drips content of effective and is 3.5% acid KClO of xylogen quality
3With mass content be 4 ‰ ZnCl of xylogen quality
2After, reaction 1h obtains the xylogen carboxylate salt; 0.1mol aminoethyl piperazine is dissolved into the ethanol liquid of 25ml, the formaldehyde that under 20 ° of C, drips 0.1mol is in above-mentioned solution, and reaction 1h obtains intermediate A solution under 30 ° of C; Secondly middle A drips of solution is added among the xylogen carboxylic acid salt solution, elevated temperature to 50 ° C reacts 5.5h and obtains the xylogen anionic emulsifier then.Recording the lignin conversion rate through liquid chromatography is 79.3%, and thick liquid stays does the experiment of preparation emulsified bitumen.
Take by weighing 4g polyoxyethylene nonylphenol (EO=40 earlier; Producer: the g AR of Shanghai Heng Ji chemical industry International Trading Company Ltd) adds 55 ° of C warm water 100g and makes its solution, again to wherein adding the above-mentioned self-control xylogen of 40g emulsifying agent; Water is to 350g then, drips 30% NaOH (commercially available) to the PH=11.Add water to 400g at last, give over to emulsified bitumen.
Take by weighing earlier 40g LA (producer: the xylogen emulsifying agent real dimension gram of virtue dimension), add a certain amount of water then to 350g, drip 30% NaOH (commercially available) to the PH=11.Add water to 400g at last, give over to emulsified bitumen.
Get SK70# pitch (Jiangyin Golden Leaf Products Co., Ltd) 600g, be heated to 140 ° of C.Above-mentioned soap lye 400g is heated to 60 ° of C, through colloidal mill (model: DSH100 processing parameter: mill spacing 0.015mm, rotating speed 2000r/min) preparation bitumen emulsion.Obtain even, fine and smooth negatively charged ion and split slow-setting emulsified asphalt slowly.
The preparation of CA mortar: siccative (Jiangsu Botexin Materials Co., Ltd) the preheating 24h under 50 ° of C that gets 2000g.Add emulsified bitumen 320g in the restir pot.Take by weighing DF201 type skimmer (Jiangsu Botexin Materials Co., Ltd) 0.15g, PCA-RX water reducer (Jiangsu Botexin Materials Co., Ltd) 3.5g adds water to 185g.The above-mentioned aqueous solution is joined respectively in the emulsified bitumen pot stirring at a slow speed under the 2min (60r/min) with gathering materials, stirs 3min (200r/min) fast, after stir 2min (60r/min) at a slow speed, survey 0min, 30min, 1h, 2h, 3h, 4h, flow cone time.Need in the thermostat container of 50 ° of C, to be incubated after each the measurement.Table 6 is the performance evaluation table of emulsifying agent.
The performance evaluation of table 6 emulsifying agent
Embodiment 7
The mass content that drips effective constituent among the real dimension gram of 40% virtue dimension xylogen (virtue is tieed up real Virbac) the alkaline solution 100g with PH=10.5 is after 4.5% ydrogen peroxide 50 and the mass content of xylogen quality is 5 ‰ KBr of xylogen quality; Be warmed up to 60 ° of C; Reaction 2h obtains the xylogen carboxylate salt; 0.1mol piperazine dissolved is to the ethanol liquid of 25ml, the formaldehyde that under 10 ° of C, drips 0.15mol is in above-mentioned solution, and reaction 3h obtains intermediate A solution under 15 ° of C; Secondly middle A drips of solution is added among the xylogen carboxylic acid salt solution, reduces the temperature to 30 ° of C then, reaction 7h obtains the xylogen anionic emulsifier.Recording the lignin conversion rate through liquid chromatography is 84.4%, and thick liquid stays does the experiment of preparation emulsified bitumen.
Take by weighing 4g polyoxyethylene nonylphenol (EO=40 earlier; Producer: the g AR of Shanghai Heng Ji chemical industry International Trading Company Ltd); Add 55 ° of C warm water 100g and make its solution; To wherein adding the above-mentioned self-control xylogen of 28g emulsifying agent, add water to 350g then again, drip 30% NaOH (commercially available) to the PH=11.Add water to 400g at last, give over to emulsified bitumen.
Take by weighing earlier 28g LA (producer: the xylogen emulsifying agent real dimension gram of virtue dimension), add a certain amount of water then to 350g, drip 30% NaOH (commercially available) to the PH=11.Add water to 400g at last, give over to emulsified bitumen.
Get SK70# pitch (Jiangyin Golden Leaf Products Co., Ltd) 600g, be heated to 140 ° of C.Above-mentioned soap lye 400g is heated to 60 ° of C, through colloidal mill (model: DSH100 processing parameter: mill spacing 0.015mm, rotating speed 2000r/min) preparation bitumen emulsion.Obtain even, fine and smooth negatively charged ion and split slow-setting emulsified asphalt slowly.
The preparation of CA mortar: siccative (Jiangsu Botexin Materials Co., Ltd) the preheating 24h under 50 ° of C that gets 2000g.Add emulsified bitumen 320g in the restir pot.Take by weighing DF201 type skimmer (Jiangsu Botexin Materials Co., Ltd) 0.15g, PCA-RX water reducer (Jiangsu Botexin Materials Co., Ltd) 3.5g adds water to 185g.The above-mentioned aqueous solution is joined respectively in the emulsified bitumen pot stirring at a slow speed under the 2min (60r/min) with gathering materials, stirs 3min (200r/min) fast, after stir 2min (60r/min) at a slow speed, survey 0min, 30min, 1h, 2h, 3h, 4h, flow cone time.Need in the thermostat container of 50 ° of C, to be incubated after each the measurement.Table 7 is the performance evaluation table of emulsifying agent.
The performance evaluation of table 7 emulsifying agent
Claims (8)
1. high temperature tolerance xylogen asphalt emulsifier is characterized in that making as follows:
A, with amine, solvent and aldehyde under 10 ° of C～30 ° C, reaction 1～3h, wherein, every mole of amine needs the 0-50ml solvent, the mol ratio of amine and aldehyde is 1:1～1:5;
B, be that 25-40%, Ph add metal ion compound and oxygenant in the xylogen alkaline solution of 8-11 with mass concentration; Under 60 ° of C～100 ° C; Reaction 1～5h, wherein, the quality consumption of metal ion compound is the 1-5 ‰ of xylogen quality; The quality consumption of oxygenant is the 3.5-10% of xylogen quality, and wherein per 0.1 mole of amine needs the 25-40g xylogen;
C, will go up steps A and step B products therefrom and mix, under 30 ° of C～70 ° C, reaction 3-7h;
Above-mentioned amine is diethylolamine, aminoethyl piperazine, piperazine or NH
2(CH
2CH
2NH)
nThe mixture of any proportioning of one or more among the H, wherein n is not more than 6 natural number; Aldehyde does
R
1Alkyl or aromatic base for H, no α H; Solvent is methyl alcohol, ethanol or water.
2. high temperature tolerance xylogen asphalt emulsifier as claimed in claim 1 is characterized in that: said oxygenant is ydrogen peroxide 50, O
3, KClO
3, KMnO
4Or Na
2O
2In the mixture of one or more any proportionings.
3. according to claim 1 or claim 2 a kind of high temperature tolerance xylogen asphalt emulsifier, it is characterized in that: described metal ion compound is FeCl
3, FeSO
4, CuSO
4, MnO
2, ZnSO
4, ZnCl
2Or the mixture of one or more any proportionings among the KBr.
4. according to claim 1 or claim 2 high temperature tolerance xylogen asphalt emulsifier is characterized in that: R in the said aldehyde
1Be H, phenyl or butyl.
5. according to claim 1 or claim 2 high temperature tolerance xylogen asphalt emulsifier, it is characterized in that: the quality consumption of said metal ion compound is the 2-3 ‰ of xylogen quality.
6. the preparation method of any described high temperature tolerance xylogen asphalt emulsifier of claim 1 to 5 is characterized in that comprising the steps:
A, with amine, solvent and aldehyde under 10 ° of C～30 ° C, reaction 1～3h, wherein, every mole of amine needs the 0-50ml solvent, the mol ratio of amine and aldehyde is 1:1～1:5;
B, be that 25-40%, Ph add metal ion compound and oxygenant in the xylogen alkaline solution of 8-11 with mass concentration; Under 60 ° of C～100 ° C; Reaction 1～5h, wherein, the quality consumption of metal ion compound is the 1-5 ‰ of xylogen quality; The quality consumption of oxygenant is the 3.5-10% of xylogen quality, and wherein per 0.1 mole of polyamine needs the 25-40g xylogen;
C, will go up steps A and step B products therefrom is blended under 30 ° of C～70 ° C, reaction 3-7h;
Above-mentioned amine is diethylolamine, aminoethyl piperazine, piperazine or NH
2(CH
2CH
2NH)
nThe mixture of any proportioning of one or more among the H, wherein n is not more than 6 natural number; Aldehyde does
R
1Alkyl or aromatic base for H, no α H; Solvent is methyl alcohol, ethanol or water.
7. the application of any described high temperature tolerance xylogen asphalt emulsifier of claim 1 to 5, it is characterized in that: its consumption is the 2-6% of emulsified bitumen quality.
8. contain the emulsified bitumen that right requires 1 to 5 any described high temperature tolerance xylogen asphalt emulsifier.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103102493A (en) * | 2013-01-21 | 2013-05-15 | 江苏博特新材料有限公司 | High-temperature resistant lignin cation asphalt emulsifier and preparation method and application thereof |
| CN104530445A (en) * | 2014-12-16 | 2015-04-22 | 辽宁路通化工有限公司 | Preparation method of slow-breaking quick-setting asphalt emulsifier |
| CN106701045A (en) * | 2016-12-06 | 2017-05-24 | 江苏苏博特新材料股份有限公司 | Efficient plugging-type drilling fluid anti-caving agent as well as production method and use method thereof |
| CN114456759A (en) * | 2022-01-26 | 2022-05-10 | 山东大唐宅配家居有限公司 | High-strength environment-friendly multilayer composite board and preparation method thereof |
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| US4562236A (en) * | 1984-12-14 | 1985-12-31 | Reed Lignin Inc. | Reaction product of lignosulfonate and unsaturated fatty amine |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103102493A (en) * | 2013-01-21 | 2013-05-15 | 江苏博特新材料有限公司 | High-temperature resistant lignin cation asphalt emulsifier and preparation method and application thereof |
| CN103102493B (en) * | 2013-01-21 | 2015-02-25 | 江苏苏博特新材料股份有限公司 | High-temperature resistant lignin cation asphalt emulsifier and preparation method and application thereof |
| CN104530445A (en) * | 2014-12-16 | 2015-04-22 | 辽宁路通化工有限公司 | Preparation method of slow-breaking quick-setting asphalt emulsifier |
| CN104530445B (en) * | 2014-12-16 | 2016-09-07 | 辽宁路通化工有限公司 | A kind of preparation method splitting fast solidifying type asphalt emulsifier slowly |
| CN106701045A (en) * | 2016-12-06 | 2017-05-24 | 江苏苏博特新材料股份有限公司 | Efficient plugging-type drilling fluid anti-caving agent as well as production method and use method thereof |
| CN106701045B (en) * | 2016-12-06 | 2020-08-07 | 江苏苏博特新材料股份有限公司 | Efficient plugging type drilling fluid anti-collapse agent, production method and use method thereof |
| CN114456759A (en) * | 2022-01-26 | 2022-05-10 | 山东大唐宅配家居有限公司 | High-strength environment-friendly multilayer composite board and preparation method thereof |
| CN114456759B (en) * | 2022-01-26 | 2023-07-18 | 山东大唐宅配家居有限公司 | High-strength environment-friendly multilayer composite board and preparation method thereof |
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|---|---|
| CN102746516B (en) | 2014-09-17 |
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