CN102872753B - Surfactant composition and preparation method thereof - Google Patents
Surfactant composition and preparation method thereof Download PDFInfo
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- CN102872753B CN102872753B CN201210421415.7A CN201210421415A CN102872753B CN 102872753 B CN102872753 B CN 102872753B CN 201210421415 A CN201210421415 A CN 201210421415A CN 102872753 B CN102872753 B CN 102872753B
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Abstract
The invention provides a surfactant composition comprising the following components in weight percent: 5-12% of fatty acid alkanolamide polyoxyethylene ether glucoside, 5-15% of fatty acid alkanolamide polyoxyethylene ether glucoside carboxylate and 16-37% of any one or mixture of two of dipolymers of the fatty acid alkanolamide polyoxyethylene ether glucoside and the fatty acid alkanolamide polyoxyethylene ether glucoside carboxylate. The invention further provides a method for preparing a surfactant mixture by using corn straws. The surfactant disclosed by the invention is low in cost and simple in process; an alkyl glucoside derivative, namely a novel surfactant, production process and a product are green and environmentally-friendly; raw materials have small dependence on petroleum, the investment of equipment for production is small and a complicated separation procedure does not need to be carried out; and the surface activity performance and the efficiency of the product are greatly improved, the use temperature range of the product is wide, the tolerance of the product to an electrolyte is strong, the greasy dirt removing capability is extremely strong and the hard water resisting effect is good.
Description
Technical field
The invention belongs to surfactant production technical field, relate in particular to a kind of surfactant mixture containing APG derivative of being prepared by maize straw, and preparation method thereof.
Background technology
Maize straw resource is abundant, genus renewable resource, with low cost, and in numerous areas, people are very active to its research.And in surfactant agent industry, people are seeking raw material abundance, process safety, environmental protection, excellent performance, new product with low cost always.A large amount of surfactants that use have at present: alkyl benzene sulphonate, AES, APES series, AEO series and cation and amphoteric surfactant, and of a great variety; The surfactant that industrial circle is conventional is that non-ionic surface active agent is main.Wherein, NPE class performance is good, cost is moderate, but in product, contains phenyl ring, belongs to non-environmentally friendly machine; Fatty alcohol polyethenoxy ether class performance is slightly poor compared with NPE class, and some field application performance does not reach requirement, and cost is moderate, belongs to environmentally friendly machine; Isomery alcohol polyethenoxy ether class, performance is best, belongs to environmentally friendly machine, and cost is very high; Alcohol ether carboxylate AEC, alcohol ether phosphate monoester PNP belong to new green environment protection type surfactant, and performance is fine; APG(APG), belong to state-of-the art environmental protection surfactant, excellent performance, and there are a lot of not available properties of other surfactant, the raw material using belongs to the resource of natural reproducible, but maximum shortcoming is that production cost is much higher than common surfactant, thereby application is also only in part high-end field, the position of the market share in pyramid point.Therefore need to develop that a kind of cost is low, technical process is simple, easy operating, production process safety and environmental protection, Product Green environmental protection, excellent performance, widely used infant industry surfactant.
Summary of the invention
The present invention be intended to overcome the deficiencies in the prior art part and provide that a kind of cost is low, technical process is simple, easy operating, production process safety and environmental protection, Product Green environmental protection, excellent performance, widely used industrial surface activity agent.
For solving the problems of the technologies described above, the present invention is achieved in that
A kind of surfactant mixture is provided, according to weight percent meter, it contains 5 ~ 12% fatty acid alkanol amides polyoxyethylene ether glucosides, 5 ~ 15% fatty acid alkanol amides polyoxyethylene ether glucosides carboxylate, and the dimeric mixture of any one or two kinds in 16 ~ 37% fatty acid alkanol amides polyoxyethylene ether glucosides and fatty acid alkanol amides polyoxyethylene ether glucosides carboxylate.
Described fatty acid alkanol amides polyoxyethylene ether glucosides preferred structure is suc as formula the compound shown in (1), wherein, the hydrocarbon chain that R is C11-17, the integer of n=3 ~ 5, and the rational of m=1 ~ 5:
Described fatty acid alkanol amides polyoxyethylene ether glucosides carboxylate preferred structure is suc as formula the compound shown in (2), wherein, the hydrocarbon chain that R is C11-17, the integer of n=3 ~ 5, and the rational of m=1 ~ 5:
The dimer of any one in described fatty acid alkanol amides polyoxyethylene ether glucosides and fatty acid alkanol amides polyoxyethylene ether glucosides carboxylate or two kinds, comprises the dimer that mixes of fatty acid alkanol amides polyoxyethylene ether glucosides dimer, fatty acid alkanol amides polyoxyethylene ether glucosides carboxylate dimer or fatty acid alkanol amides polyoxyethylene ether glucosides and fatty acid alkanol amides polyoxyethylene ether glucosides carboxylate.
Described fatty acid alkanol amides polyoxyethylene ether glucosides dimer preferred structure is suc as formula the compound shown in (3):
Described fatty acid alkanol amides polyoxyethylene ether glucosides carboxylate dimer preferred structure is suc as formula the compound shown in (4):
Described fatty acid alkanol amides polyoxyethylene ether glucosides and fatty acid alkanol amides polyoxyethylene ether glucosides carboxylate mix dimer preferred structure suc as formula the compound shown in (5):
In above-mentioned formula (3) ~ (5),
R is the hydrocarbon chain of C11-17;
R
1for
Or-CH
2-CH
2-;
The integer of n=3 ~ 5, and the rational of m=1 ~ 5.
In the preferred scheme of one of the present invention, according to weight percent meter, described surfactant mixture contains:
Fatty acid alkanol amides polyoxyethylene ether glucosides 5 ~ 12%, fatty acid alkanol amides polyoxyethylene ether glucosides carboxylate 5 ~ 15%, fatty acid alkanol amides polyoxyethylene ether glucosides dimer 5 ~ 12%, fatty acid alkanol amides polyoxyethylene ether glucosides carboxylate dimer 4 ~ 10% and fatty acid alkanol amides polyoxyethylene ether glucosides and fatty acid alkanol amides polyoxyethylene ether glucosides carboxylate mix dimer 7 ~ 15%.
In another preferred version of the present invention, according to weight percent meter, described surfactant mixture further contains 4 ~ 10% fatty acid alkanol amides polyoxyethylene and 3 ~ 8% fatty acid alkanol amides polyethenoxy ether carboxylate.
In another preferred scheme of the present invention, described surfactant mixture prepares take maize straw as raw material.
The present invention also provides a kind of method of preparing described surfactant mixture, comprises the following steps:
1) in the maize straw of pulverizing, add low-carbon alcohols and catalyst to carry out cellulose degradation reaction, the weight ratio that feeds intake of low-carbon alcohols and maize straw is 1:1 ~ 8:1, preferably 3:1 ~ 5:1, the addition of catalyst is 0.1% ~ 3% of maize straw weight, preferably 0.5% ~ 1.5%, reaction temperature is 80 ~ 180 ℃, preferably 120 ~ 140 ℃, the reaction time is 0.5 ~ 5h, preferably 0.5 ~ 2h, by reacted material Separation of Solid and Liquid, obtain the liquid phase material 1 and the remaining solid material 1 that contain low-carbon alcohols APG;
2) solid material 1 step 1) being obtained is washed, and then the aqueous solution after washing is thoroughly dewatered through concentrated, obtains liquid phase material 2, i.e. low-carbon alcohols APG solution;
3) liquid phase material 1 and the step 2 that step 1) are obtained) liquid phase material 2 that the obtains concentration that is concentrated into low-carbon alcohols APG after merging reaches 20 ~ 95%, and preferably 50 ~ 60%, obtain liquid phase material 3;
4) in the liquid phase material 3 obtaining in step 3), add the compound that contains lipophilic group carbochain, add catalyst simultaneously; The mass ratio of the low-carbon alcohols APG in the compound that contains lipophilic group carbochain and the liquid phase material 3 adding is 1:1 ~ 1:15, preferably 1:3 ~ 1:5; The addition of catalyst is 0.1% ~ 5% of pure low-carbon alcohols glucosides quality, preferably 0.5% ~ 1.0%; Reaction temperature is 80 ~ 200 ℃, preferably 10 ~ 130 ℃; Under vacuum, react, residual voltage is 0.001 ~ 0.05MPa, preferably 0.005 ~ 0.01Mpa; Reaction time is 0.5 ~ 15h, preferably 3 ~ 5h; Reaction finishes rear neutralization reaction product to pH=8 ~ 10;
5) product step 4) the being obtained processing of decolouring, then adds water and obtains the long alkyl chain length glucosides solution of 50% solid content;
6) in the solution obtaining in step 5), add catalyst and pass into air and carry out oxidation reaction; The addition of catalyst is 0.1% ~ 5% of APG quality, preferably 0.5% ~ 1.0%; Reaction temperature is 40 ~ 140 ℃, preferably 60 ~ 90 ℃; Reaction pressure 0.005 ~ 0.03MPa, reaction time 0.5 ~ 10h, preferably 2 ~ 6h, keeps pH value of reaction system 2 ~ 10 in course of reaction, and preferably 4 ~ 6; Obtain the product mixed solution that contains APG carboxylate;
7) in the reacted mixed solution obtaining in step 6), add coupling agent to carry out condensation reaction, make APG and carboxylate derivatives thereof in solution form dimer, the addition of coupling agent is 3 ~ 15% of pure APG derivative quality, reaction temperature is 50 ~ 150 ℃, reaction time is 1 ~ 3 hour, the pH value of reaction system is controlled in 6 ~ 10 scope, finally obtains surfactant mixture of the present invention.
Low-carbon alcohols described in step 1) can be selected from the one in methyl alcohol, ethanol, butanols, ethylene glycol, propane diols or glycerine, preferably ethylene glycol or propane diols.
Catalyst described in step 1) can be selected from the one in p-methyl benzenesulfonic acid, alkyl sulfonic acid, sulfuric acid or phosphoric acid, preferably p-methyl benzenesulfonic acid.
Step 2) described washing preferred version is: washing times is 1 ~ 8 time, preferably 2 ~ 4 times; Each water consumption is 10% ~ 150 of maize straw quality, preferably 30% ~ 50%; Each washing time is 5 ~ 60 minutes, preferably 10 ~ 40 minutes.
Step 2) the described aqueous solution after washing is concentrated, be first concentrated through permeable membrane dehydration, and then carry out decompression distillation and thoroughly dewater.Described reduced pressure distillation process condition comprises: temperature is 50 ~ 160 ℃, preferably 80 ~ 120 ℃; Pressure is 0.01 ~ 0.09Mpa, preferably 0.04 ~ 0.06Mpa.
Concentrated preferred vacuum distillation method described in step 3), vapo(u)rizing temperature is 80 ~ 200 ℃, preferably 110 ~ 140 ℃; Vacuum is residual voltage 0.002 ~ 0.09MPa, preferably 0.01 ~ 0.03Mpa.
The compound that contains lipophilic group carbochain described in step 4) can be selected from 8 ~ 10 carbon alcohol, 12 ~ 14 carbon alcohol, 16 ~ 18 carbon alcohol, isomerous tridecanol, lauric monoethanolamide or oleic acid single ethanol amide, or the ethoxylated product of these materials; The adduct number of the oxirane of the ethoxylated product of these described materials is can be 0 ~ 15, preferably 2-5.
Catalyst described in step 4) can be selected from sulfuric acid, phosphoric acid, p-methyl benzenesulfonic acid, sulfosuccinic acid or solid acid catalyst SO
4-/ZrO
2, SO
4-/S-Zr-Ti or SO
4any one in-/Ti-La-O.
During decolouring described in step 5) is processed, decolorizer can be selected from hydrogen peroxide, sodium perborate, sodium peroxydisulfate, clorox or sodium sulfite; The addition of described decolorizer accounts for 0.5% ~ 15% of APG quality, and preferably 3% ~ 6%; Bleaching temperature is 50 ~ 120 ℃, preferably 70 ~ 90 ℃; Bleaching time is 0.1 ~ 3h, preferably 0.5 ~ 1h.
Solid acid catalyst described in step 6) can be selected from one or more the mixture in the catalyst such as commercially available Pd/C, Pd-Bi/C, Pd-Sr/C, Pd-La/C.
Coupling agent described in step 7) can be polynary halogenated organic compounds, for example, can be selected from dichloroethanes, the two monoxone acid amides of ethylenediamine or ethylene glycol bis chloracetate; The preferably two monoxone acid amides of ethylenediamine.
It is raw material that the present invention adopts maize straw with low cost, utilize high efficiency straw degradative method, succinct degradation product separating technology, by improving and the synthetic process of optimizing, synthesize midbody product APG, and this APG does not need to separate, directly carry out next step reaction and synthesize and expect the APG derivative novel surfactant product of molecular structure.This novel surfactant production technology and the product of producing be environmental type, raw materials used to oil rely on little, produce that equipment needed thereby investment surface-active usefulness and efficiency little, that do not need to carry out complex separations operation, product improve greatly, product serviceability temperature wide ranges, product to electrolytical tolerance by force, wipe oil ability is strong, anti-hard water usefulness is good; Production cost obviously reduces, its production cost is starkly lower than the surfactants such as APES series of the prior art, AEO series, AES, alkyl benzene sulphonate, compared with surfactant costs 40% such as APG APG, AEC, PNP; This novel surfactant is with the advantage of its good combination property, low cost, environmental protection, and, environmental protection efficient as one, infant industry surfactant, have wide market prospects and huge market potential.
The application category of surfactant mixture of the present invention comprises: many industrial circles such as textile printing and dyeing, the industry cleaning link energy, petrochemical industry, mining, electric power, textile printing and dyeing, machine-building, leather, papermaking, communications and transportation, agricultural, medicine, bioengineering and fabrication of new materials, microemulsion Chemical Reaction Engineering, molecular level electronic devices and components high-technology field.
The surfactant mixture product of preparing take the embodiment of the present invention 1 is below example, proves that product of the present invention has good performance and effect compared with existing product:
One, activating agent key property test data (in table 1):
Table 1.
| Critical micelle concentration mg/L | Surface tension mN/m | |
| Mixture 1 prepared by embodiment 1 | 28 | 24 |
| NP-10 | 52 | 27.5 |
| AEO9 | 58 | 29 |
| APG（C1214） | 61 | 26 |
Two, activating agent using property data test data:
1. the performance indications of testing under normal concentration and the comparison of other surfactant product of the prior art, in table 2:
Table 2.
2. the performance data of testing under the embodiment of the present invention 1 product variable concentrations, in table 3
Table 3
Three, the performance indications correction data of product of the present invention and prior art products is analyzed:
1, use as metal cleaner, compared with NPE (NP-10), AEO AEO9, APG, product of the present invention reduces 20 ~ 30% in the situation that adding dosage, still can reach same degreasing rate and cleaning performance, and rustless property is obviously good.
2, use as textile printing and dyeing industry cleaning agent, compared with NPE (NP-10), AEO AEO9, APG, product of the present invention reduces 20 ~ 25% in the situation that adding dosage, still can reach same detergency and cleaning performance.
3, for civilian liquid detergent, washing powder and public utility cleaning agent various cleaning agents such as () hotel sheet, the tablecloth, carpet, glass formula, good with surfactant compatibilities such as AES, sodium alkyl benzene sulfonate, AEO9, AEC, significantly liquid detergent cost and reach same or slightly high detergency, to the hardness better adaptability of water quality, in the high water quality of hardness, have more advantage, and clothing pliability after washing improves.
The specific embodiment
Embodiment 1
With bale opener by maize straw Bales Off, process pulverizer is by corn straw smashing, be transported to storage bin, through transport tape, corn stalk powder is transported to 4000kg measuring tank from storage bin, then corn stalk powder is put into low-carbon alcohols glycosylation reaction still (1# still), added 16000kg ethylene glycol by measuring pump, add the catalyst p-methyl benzenesulfonic acid 32kg weighing, at the temperature of 160 ℃, react 1.5 hours, reacted material is forwarded in centrifuge, isolate liquid phase material, liquid material is proceeded to 1# storage tank stores, then use 800kg, washing 15 minutes, the centrifugal dehydration 10 minutes of 70 ℃, the water after washing deposits 2# storage tank in, and repeat this operation and wash altogether 3 times, the solid material after washing, dry through rotary drum dryer, pack warehouse-in, from 2# storage tank, the aqueous solution wash-out is first concentrated through permeable membrane dehydration, then squeeze into dehydrating kettle (2# still) with pump, at the temperature of 95 ℃, the vacuum of-0.03MPa, distillation dehydration 1.5 hours, material after dehydration distillation is sent into 1# storage tank, from 1# storage tank, material is squeezed into concentration kettle (3# still) with pump, the temperature of 145 ℃, the vacuum of-0.08MPa, the de-ethylene glycol of distillation 2.5 hours, material after concentrated is sent into APG and prepare still (4# still), in 4# still, add palm oil fatty acid list isopropanol amide APEO (ethoxymer distribution is 3) 1200kg, catalyst amber sulfonic acid 10kg, the temperature of 120 ℃, under-0.096MPa vacuum degree condition, react 3.5 hours, in 4# still, add nertralizer magnesia 25kg, stir 0.5 hour, in 4# still, drip (dripping off for 30 minutes) decolorizer hydrogen peroxide 80kg, the temperature of 80 ℃, reaction 1.5 hours, in 4# still, add 2400kg water, stir 0.5 hour, obtain the APG of 50% solid content, the APG of 4# still 50% solid content is transferred to APG derivative to be prepared in still (5# still), add catalyst compound solid-acid 22kg, by roots blower to the air that passes into purification in 5# still, the temperature of 75 ℃, under 0.015MPa pressure condition, react 5 hours, by setting the numerical value of pH transmission system signal, guarantee that to the sodium hydroxide solution of automatic dripping 30% in reactor pH value of reaction system is in 4 ~ 6 scope, use filter filtering recovering catalyst, for reuse (reusable 20 ~ 30 times) later, add the two monoxone acid amides 80kg of coupling agent ethylenediamine, in the temperature of 85 ° of C, the pH value of reaction system is controlled in 8 ~ 9 scope, react 2 hours, obtain final products---the surfactant mixture 1 that contains double type APG derivative, concrete constituent content is as follows:
1, the polyoxyethylated mixture of fatty acid alkanol amides that structure is following, 6.5%
This mixture is that in above formula, R is C
15h
31hydrocarbon chain and the compound of n=4 and above formula in R be C
17h
33hydrocarbon chain and the mixture of the compound of n=4;
The mixture of the fatty acid alkanol amides APEO carboxylic acid sodium that 2, structure is following, 3.5%
The mixture of the fatty acid alkanol amides polyoxyethylene ether glucosides that 3, structure is following, 12%
4, the fatty acid alkanol amides polyoxyethylene ether glucosides carboxylic acid sodium mixture that structure is following, 10%
5, fatty acid alkanol amides polyoxyethylene ether glucosides dimer (double type surfactant) mixture that structure is following, 5%
The mixture of the fatty acid alkanol amides polyoxyethylene ether glucosides carboxylic acid sodium dimer (double type surfactant) that 6, structure is following, 4.5%
7, the fatty acid alkanol amides polyoxyethylene ether glucosides that structure is following and fatty acid alkanol amides polyoxyethylene ether glucosides carboxylate mix dimeric compound, 8.5%
wherein R, R
1, n and m definition the same;
8, other components (inorganic salts, low-carbon alcohols glucosides etc.), 3%
9, water, 47%
Embodiment 2
With bale opener by maize straw Bales Off, process pulverizer is by corn straw smashing, be transported to storage bin, through transport tape, corn stalk powder is transported to 4000kg measuring tank from storage bin, then corn stalk powder is put into low-carbon alcohols glycosylation reaction still (1# still), added 15000kg ethylene glycol by measuring pump, add the catalyst p-methyl benzenesulfonic acid 30kg weighing, at the temperature of 160 ℃, react 2 hours, reacted material is forwarded in centrifuge, isolate liquid phase material, liquid material is proceeded to 1# storage tank stores, then use 800kg, washing 15 minutes, the centrifugal dehydration 10 minutes of 70 ℃, water after washing deposits 2# storage tank in, repeats this operation and washes altogether 3 times, the solid material after washing, dry through rotary drum dryer, pack warehouse-in, from 2# storage tank, the aqueous solution wash-out is first concentrated through permeable membrane dehydration, then squeeze into dehydrating kettle (2# still) with pump, at the temperature of 90 degree, the vacuum of-0.04MPa, distillation dehydration 1.5 hours, material after dehydration distillation is sent into 1# storage tank, from 1# storage tank, material is squeezed into concentration kettle (3# still) with pump, the temperature of 145 ℃, the vacuum of-0.08MPa, the de-ethylene glycol of distillation 2.5 hours, material after concentrated is sent into APG and prepare still (4# still), in 4# still, add laurate list isopropanol amide APEO (ethoxymer distribution is 3) 1000kg, catalyst amber sulfonic acid 10kg, the temperature of 120 ℃, under-0.096MPa vacuum degree condition, react 3.5 hours, in 4# still, add nertralizer magnesia 25kg, stir 0.5 hour, in 4# still, drip (dripping off for 30 minutes) decolorizer hydrogen peroxide 80kg, the temperature of 80 ℃, reaction 1.5 hours, in 4# still, add 2000kg water, stir 0.5 hour, obtain the APG of 50% solid content, the APG of 4# still 50% solid content is transferred to APG derivative to be prepared in still (5# still), add catalyst compound solid-acid 20kg, by roots blower to the air that passes into purification in 5# still, the temperature of 75 ℃, under 0.015MPa pressure condition, react 5 hours, by setting the numerical value of pH transmission system signal, guarantee that to the sodium hydroxide solution of automatic dripping 30% in reactor pH value of reaction system is in 4 ~ 6 scope, use filter filtering recovering catalyst, for reuse (reusable 20 ~ 30 times) later, add the two monoxone acid amides 100kg of coupling agent ethylenediamine, in the temperature of 80 ° of C, the pH value of reaction system is controlled in 8 ~ 9 scope, react 2.5 hours, obtain final products---the surfactant mixture 2 that contains double type APG derivative, concrete constituent content is as follows.
1, the fatty acid alkanol amides polyoxyethylene that structure is following, 7%
2, the fatty acid alkanol amides polyethenoxy ether carboxylate that structure is following, 4%
3, the fatty acid alkanol amides polyoxyethylene ether glucosides that structure is following, 10%
4, the fatty acid alkanol amides polyoxyethylene ether glucosides carboxylate that structure is following, 8%
5, the fatty acid alkanol amides polyoxyethylene ether glucosides dimer (double type surfactant) that structure is following, 6%
wherein R, m and n definition are the same, R
1for
6, the fatty acid alkanol amides polyoxyethylene ether glucosides carboxylate dimer (double type surfactant) that structure is following, 5%
7, the fatty acid alkanol amides polyoxyethylene ether glucosides that structure is following and fatty acid alkanol amides polyoxyethylene ether glucosides carboxylate mix dimer, 10%
8, other components (inorganic salts, low-carbon alcohols glucosides etc.), 3.4%
9, water, 46.6%
Embodiment 3
With bale opener by maize straw Bales Off, process pulverizer is by corn straw smashing, be transported to storage bin, through transport tape, corn stalk powder is transported to 4000kg measuring tank from storage bin, then corn stalk powder is put into low-carbon alcohols glycosylation reaction still (1# still), added 18000kg ethylene glycol by measuring pump, add the catalyst p-methyl benzenesulfonic acid 35kg weighing, at the temperature of 150 ℃, react 1.5 hours, reacted material is forwarded in centrifuge, isolate liquid phase material, liquid material is proceeded to 1# storage tank stores, then use 600kg, washing 15 minutes, the centrifugal dehydration 10 minutes of 70 ℃, water after washing deposits 2# storage tank in, repeats this operation and washes altogether 3 times, the solid material after washing, dry through rotary drum dryer, pack warehouse-in, from 2# storage tank, the aqueous solution wash-out is first concentrated through permeable membrane dehydration, then squeeze into dehydrating kettle (2# still) with pump, at the temperature of 95 ℃, the vacuum of-0.03MPa, distillation dehydration 1.5 hours, material after dehydration distillation is sent into 1# storage tank, from 1# storage tank, material is squeezed into concentration kettle (3# still) with pump, the temperature of 145 ℃, the vacuum of-0.08MPa, the de-ethylene glycol of distillation 2.5 hours, material after concentrated is sent into APG and prepare still (4# still), in 4# still, add palm oil fatty acid list isopropanol amide APEO (ethoxymer distribution is 4) 1100kg, catalyst amber sulfonic acid 10kg, the temperature of 120 ℃, under-0.096MPa vacuum degree condition, react 3.5 hours, in 4# still, add nertralizer magnesia 25kg, stir 0.5 hour, in 4# still, drip (dripping off for 30 minutes) decolorizer hydrogen peroxide 90kg, the temperature of 90 ℃, reaction 1.5 hours, in 4# still, add 2200kg water, stir 0.5 hour, obtain the APG of 50% solid content, the APG of 4# still 50% solid content is transferred to APG derivative to be prepared in still (5# still), add catalyst compound solid-acid 24kg, by roots blower to the air that passes into purification in 5# still, the temperature of 75 ℃, under 0.02MPa pressure condition, react 4 hours, by setting the numerical value of pH transmission system signal, guarantee that to the sodium hydroxide solution of automatic dripping 30% in reactor pH value of reaction system is in 4 ~ 6 scope, use filter filtering recovering catalyst, for reuse (reusable 20 ~ 30 times) later, add coupling agent ethylene glycol bis chloracetate 110kg, in the temperature of 75 ° of C, the pH value of reaction system is controlled in 8 ~ 9 scope, react 3 hours, obtain final products---the surfactant mixture 3 that contains double type APG derivative, concrete constituent content is as follows:
1, the fatty acid alkanol amides polyoxyethylene mixture that structure is following, 8.5%
This mixture is that in above formula, R is C
15h
31hydrocarbon chain and the compound of n=5 and above formula in R be C
17h
33hydrocarbon chain and the mixture of the compound of n=5;
The mixture of the fatty acid alkanol amides polyethenoxy ether carboxylate that 2, structure is following, 3.5%
The mixture of the fatty acid alkanol amides polyoxyethylene ether glucosides that 3, structure is following, 8%
The mixture of the fatty acid alkanol amides polyoxyethylene ether glucosides carboxylate that 4, structure is following, 7.4%
The mixture of the fatty acid alkanol amides polyoxyethylene ether glucosides dimer (double type surfactant) that 5, structure is following, 5.6%
The mixture of the fatty acid alkanol amides polyoxyethylene ether glucosides carboxylate dimer (double type surfactant) that 6, structure is following, 6.3%
7, the fatty acid alkanol amides polyoxyethylene ether glucosides that structure is following and fatty acid alkanol amides polyoxyethylene ether glucosides carboxylate mix dimeric mixture, 10.7%
8, other components (inorganic salts, low-carbon alcohols glucosides etc.), 3.8%
9, water, 46.2%
Embodiment 4
With bale opener by maize straw Bales Off, process pulverizer is by corn straw smashing, be transported to storage bin, through transport tape, corn stalk powder is transported to 4000kg measuring tank from storage bin, then corn stalk powder is put into low-carbon alcohols glycosylation reaction still (1# still), added 16500kg propane diols by measuring pump, add the catalyst p-methyl benzenesulfonic acid 28kg weighing, at the temperature of 180 ℃, react 1 hour, reacted material is forwarded in centrifuge, isolate liquid phase material, liquid material is proceeded to 1# storage tank stores, then use 800kg, washing 15 minutes, the centrifugal dehydration 10 minutes of 70 ℃, water after washing deposits 2# storage tank in, repeats this operation and washes altogether 3 times, the solid material after washing, dry through rotary drum dryer, pack warehouse-in, from 2# storage tank, the aqueous solution wash-out is first concentrated through permeable membrane dehydration, then squeeze into dehydrating kettle (2# still) with pump, at the temperature of 95 ℃, the vacuum of-0.03MPa, distillation dehydration 1.5 hours, material after dehydration distillation is sent into 1# storage tank, from 1# storage tank, material is squeezed into concentration kettle (3# still) with pump, the temperature of 145 ℃, the vacuum of-0.08MPa, the de-propane diols of distillation 2.5 hours, material after concentrated is sent into APG and prepare still (4# still), in 4# still, add oleic acid single ethanol amide APEO (ethoxymer distribution is 2) 1150kg, catalyst amber sulfonic acid 10kg, the temperature of 120 ℃, under-0.092MPa vacuum degree condition, react 3.5 hours, in 4# still, add nertralizer magnesia 25kg, stir 0.5 hour, in 4# still, drip (dripping off for 30 minutes) decolorizer hydrogen peroxide 80kg, the temperature of 80 ℃, reaction 1.5 hours, in 4# still, add 2300kg water, stir 0.5 hour, obtain the APG of 50% solid content, the APG of 4# still 50% solid content is transferred to APG derivative to be prepared in still (5# still), add catalyst compound solid-acid 25kg, by roots blower to the air that passes into purification in 5# still, the temperature of 75 ℃, under 0.025MPa pressure condition, react 4.5 hours, by setting the numerical value of pH transmission system signal, guarantee that to the sodium hydroxide solution of automatic dripping 30% in reactor pH value of reaction system is in 4 ~ 6 scope, use filter filtering recovering catalyst, for reuse (reusable 20 ~ 30 times) later, add the two monoxone acid amides 130kg of coupling agent ethylenediamine, in the temperature of 75 ° of C, the pH value of reaction system is controlled in 8 ~ 9 scope, react 3 hours, obtain final products---the surfactant mixture 4 that contains double type APG derivative, concrete constituent content is as follows.
1, the fatty acid alkanol amides polyoxyethylene that structure is following, 6%
2, the fatty acid alkanol amides polyethenoxy ether carboxylate that structure is following, 5%
3, the fatty acid alkanol amides polyoxyethylene ether glucosides that structure is following, 8%
4, the fatty acid alkanol amides polyoxyethylene ether glucosides carboxylate that structure is following, 7%
r, m and n definition are the same,
5, the fatty acid alkanol amides polyoxyethylene ether glucosides dimer (double type surfactant) that structure is following, 6.5%
6, the fatty acid alkanol amides polyoxyethylene ether glucosides carboxylate dimer (double type surfactant) that structure is following, 5.5%
7, the fatty acid alkanol amides polyoxyethylene ether glucosides that structure is following and fatty acid alkanol amides polyoxyethylene ether glucosides carboxylate mix dimer, 12%
8, other components (inorganic salts, low-carbon alcohols glucosides etc.), 4.2%
9, water, 45.8%
Embodiment 5
With bale opener by maize straw Bales Off, process pulverizer is by corn straw smashing, be transported to storage bin, through transport tape, corn stalk powder is transported to 4000kg measuring tank from storage bin, then corn stalk powder is put into low-carbon alcohols glycosylation reaction still (1# still), added 17000kg ethylene glycol by measuring pump, add the catalyst weighing to alkyl sulfonic acid 40kg, at the temperature of 155 ℃, react 2.5 hours, reacted material is forwarded in centrifuge, isolate liquid phase material, liquid material is proceeded to 1# storage tank stores, then use 700kg, washing 15 minutes, the centrifugal dehydration 10 minutes of 85 ℃, water after washing deposits 2# storage tank in, repeats this operation and washes altogether 3 times, the solid material after washing, dry through rotary drum dryer, pack warehouse-in, from 2# storage tank, the aqueous solution wash-out is first concentrated through permeable membrane dehydration, then squeeze into dehydrating kettle (2# still) with pump, at the temperature of 85 ℃, the vacuum of-0.045MPa, distillation dehydration 1.5 hours, material after dehydration distillation is sent into 1# storage tank, from 1# storage tank, material is squeezed into concentration kettle (3# still) with pump, the temperature of 150 ℃, the vacuum of-0.07MPa, the de-ethylene glycol of distillation 2 hours, material after concentrated is sent into APG and prepare still (4# still), in 4# still, add palm oil fatty acid list isopropanol amide ethoxylate (ethoxymer distribution is 3) 1350kg, catalyst amber sulfonic acid 10kg, the temperature of 125 ℃, under-0.096MPa vacuum degree condition, react 3.5 hours, in 4# still, add nertralizer magnesia 28kg, stir 0.5 hour, in 4# still, drip (dripping off for 30 minutes) decolorizer hydrogen peroxide 100kg, the temperature of 95 ℃, reaction 1 hour, in 4# still, add 2700kg water, stir 0.5 hour, obtain the APG of 50% solid content, the APG of 4# still 50% solid content is transferred to APG derivative to be prepared in still (5# still), add catalyst compound solid-acid 32kg, by roots blower to the air that passes into purification in 5# still, at 70 ℃, under 0.02MPa pressure condition, react 4.5 hours, by setting the numerical value of pH transmission system signal, guarantee that to the sodium hydroxide solution of automatic dripping 30% in reactor pH value of reaction system is in 3.5 ~ 5.5 scope, use filter filtering recovering catalyst, for reuse (reusable 20 ~ 30 times) later, add the two monoxone acid amides 180kg of coupling agent ethylenediamine, in the temperature of 90 ° of C, the pH value of reaction system is controlled in 8 ~ 9 scope, react 3 hours, obtain final products---the surfactant mixture 5 that contains double type APG derivative, concrete constituent content is as follows, the compound structure of component 1-2 is wherein identical with the corresponding compound structure of embodiment 1, but in component 3-7 compound structure, except m=1.6, other are all identical with embodiment respective components, and the concrete ratio of each component is as follows.
1, fatty acid alkanol amides polyoxyethylene, 8%
2, fatty acid alkanol amides polyethenoxy ether carboxylate, 3%
3, fatty acid alkanol amides polyoxyethylene ether glucosides, 5%
4, fatty acid alkanol amides polyoxyethylene ether glucosides carboxylate, 4%
5, fatty acid alkanol amides polyoxyethylene ether glucosides dimer (double type surfactant), 8%
6, fatty acid alkanol amides polyoxyethylene ether glucosides carboxylate dimer (double type surfactant), 7.5%
7, fatty acid alkanol amides polyoxyethylene ether glucosides and fatty acid alkanol amides polyoxyethylene ether glucosides carboxylate mix dimer, 14.5%
8, other components (inorganic salts, low-carbon alcohols glucosides etc.), 4.9%
9, water, 45.1%
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for a person skilled in the art, the present invention can have various modifications and variations.All any modifications of doing within the spirit and principles in the present invention, be equal to replacement, improvement etc., within protection scope of the present invention all should be included in.
Claims (2)
1. a surfactant mixture, it is characterized in that: according to weight percent meter, it contains fatty acid alkanol amides polyoxyethylene ether glucosides 5～12%, fatty acid alkanol amides polyoxyethylene ether glucosides carboxylate 5～15%, fatty acid alkanol amides polyoxyethylene ether glucosides dimer 5～12%, fatty acid alkanol amides polyoxyethylene ether glucosides carboxylate dimer 4～10%, and fatty acid alkanol amides polyoxyethylene ether glucosides and fatty acid alkanol amides polyoxyethylene ether glucosides carboxylate mix dimer 7～15%, 4～10% fatty acid alkanol amides polyoxyethylene and 3～8% fatty acid alkanol amides polyethenoxy ether carboxylate,
Described fatty acid alkanol amides polyoxyethylene ether glucosides be structure suc as formula the compound shown in (1), wherein, the hydrocarbon chain that R is C11-17, the integer of n=3～5, and the rational of m=1～5;
Described fatty acid alkanol amides polyoxyethylene ether glucosides carboxylate be structure suc as formula the compound shown in (2), wherein, the hydrocarbon chain that R is C11-17, the integer of n=3～5, and the rational of m=1～5;
Described fatty acid alkanol amides polyoxyethylene ether glucosides dimer is that structure is suc as formula the compound shown in (3);
Wherein, the hydrocarbon chain that R is C11-17;
The integer of n=3～5, and the rational of m=1～5;
Described fatty acid alkanol amides polyoxyethylene ether glucosides carboxylate dimer is that structure is suc as formula the compound shown in (4);
Wherein, the hydrocarbon chain that R is C11-17;
The integer of n=3～5, and the rational of m=1～5;
Described fatty acid alkanol amides polyoxyethylene ether glucosides is that structure is suc as formula the compound shown in (5) with the dimer that mixes of fatty acid alkanol amides polyoxyethylene ether glucosides carboxylate
Wherein, the hydrocarbon chain that R is C11-17;
The integer of n=3～5, and the rational of m=1～5.
2. a method of preparing surfactant mixture claimed in claim 1, comprises the following steps:
1) in the maize straw of pulverizing, add low-carbon alcohols and catalyst to carry out cellulose degradation reaction, the weight ratio that feeds intake of low-carbon alcohols and maize straw is 1:1～8:1, the addition of catalyst is 0.1%～3% of maize straw weight, reaction temperature is 80～180 ℃, reaction time is 0.5～5h, by reacted material Separation of Solid and Liquid, obtain the liquid phase material 1 and the remaining solid material 1 that contain low-carbon alcohols APG; Described low-carbon alcohols is selected from the one in methyl alcohol, ethanol, butanols, ethylene glycol, propane diols or glycerine; Described catalyst is selected from the one in p-methyl benzenesulfonic acid, alkyl sulfonic acid, sulfuric acid or phosphoric acid;
2) solid material 1 step 1) being obtained is washed, and then the aqueous solution after washing is thoroughly dewatered through concentrated, obtains liquid phase material 2, i.e. low-carbon alcohols APG solution;
3) liquid phase material 1 and the step 2 that step 1) are obtained) liquid phase material 2 that the obtains concentration that is concentrated into low-carbon alcohols APG after merging reaches 20～95%, obtains liquid phase material 3;
4) in the liquid phase material 3 obtaining in step 3), add the compound that contains lipophilic group carbochain, add catalyst simultaneously; The mass ratio of the low-carbon alcohols APG in the compound that contains lipophilic group carbochain and the liquid phase material 3 adding is 1:1～1:15; The addition of catalyst is 0.1%～5% of pure low-carbon alcohols glucosides quality; Reaction temperature is 80～200 ℃; Under vacuum, react, residual voltage is 0.001～0.05MPa; Reaction time is 0.5～15h; Reaction finishes rear neutralization reaction product to pH=8～10; The described compound that contains lipophilic group carbochain is selected from 8～10 carbon alcohol, 12～14 carbon alcohol, 16～18 carbon alcohol, isomerous tridecanol, lauric monoethanolamide or oleic acid single ethanol amide, or the ethoxylated product of these materials; Described catalyst is selected from any one in sulfuric acid, phosphoric acid, p-methyl benzenesulfonic acid, sulfosuccinic acid or solid acid catalyst SO4-/ZrO2, SO4-/S-Zr-Ti or SO4-/Ti-La-O;
5) product step 4) the being obtained processing of decolouring, then adds water and obtains the long alkyl chain length glucosides solution of 50% solid content;
6) in the solution obtaining in step 5), add catalyst and pass into air and carry out oxidation reaction; The addition of catalyst is 0.1%～5% of APG quality; Reaction temperature is 40～140 ℃; Reaction pressure 0.005～0.03MPa, reaction time 0.5～10h, keep pH value of reaction system 2～10 in course of reaction; Obtain the product mixed solution that contains APG carboxylate; Described catalyst is selected from one or more the mixture in commercially available Pd/C, Pd-Bi/C, Pd-Sr/C, Pd-La/C;
7) in the reacted mixed solution obtaining in step 6), add coupling agent to carry out condensation reaction, described coupling agent is selected from dichloroethanes, the two monoxone acid amides of ethylenediamine or ethylene glycol bis chloracetate, make APG and carboxylate derivatives thereof in solution form dimer, the addition of coupling agent is 3～15% of pure APG derivative quality, reaction temperature is 50～150 ℃, reaction time is 1～3 hour, the pH value of reaction system is controlled in 6～10 scope, finally obtains described surfactant mixture.
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