CN102872753A - Surfactant composition and preparation method thereof - Google Patents
Surfactant composition and preparation method thereof Download PDFInfo
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- CN102872753A CN102872753A CN2012104214157A CN201210421415A CN102872753A CN 102872753 A CN102872753 A CN 102872753A CN 2012104214157 A CN2012104214157 A CN 2012104214157A CN 201210421415 A CN201210421415 A CN 201210421415A CN 102872753 A CN102872753 A CN 102872753A
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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 the surfactant production technical field, relate in particular to a kind of surfactant mixture that contains the APG derivative by the maize straw preparation, and preparation method thereof.
Background technology
Maize straw resource is abundant, genus renewable resource, with low cost, and people are very active to its research in the numerous areas.And in surfactant agent industry, people are seeking raw material abundance, process safety, environmental protection, excellent performance, new product with low cost always.At present a large amount of surfactants that use have: alkyl benzene sulphonate, AES, APES series, AEO is serial and cation and amphoteric surfactant, and is of a great variety; The surfactant that industrial circle is commonly used is that non-ionic surface active agent is main.Wherein, NPE class performance is good, cost is moderate, but contains phenyl ring in the product, belongs to non-environmentally friendly machine; The fatty alcohol polyethenoxy ether class performance is slightly poor than the 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; The APG(APG), belong to state-of-the art environmental protection surfactant, excellent performance, and have a lot of not available properties of other surfactant, the raw material that uses belongs to the resource of natural reproducible, but maximum shortcoming is that production cost is much higher than common surfactant, thereby use also only in the part high-end field, the market share is in the position of pyramid point.Therefore need that a kind of cost of exploitation is low, technical process 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 the 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), and wherein, R is the hydrocarbon chain of 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), and wherein, R is the hydrocarbon chain of 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 the 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 the 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
Perhaps-CH
2-CH
2-;
The integer of n=3 ~ 5, and the rational of m=1 ~ 5.
In a kind of preferred scheme 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 for preparing described surfactant mixture, may further comprise the steps:
1) in the maize straw of pulverizing, adds low-carbon alcohols and catalyst and carry out the cellulose degradation reaction, the weight ratio that feeds intake of low-carbon alcohols and maize straw is 1:1 ~ 8:1, preferred 3:1 ~ 5:1, the addition of catalyst is 0.1% ~ 3% of maize straw weight, preferred 0.5% ~ 1.5%, reaction temperature is 80 ~ 180 ℃, preferred 120 ~ 140 ℃, the reaction time is 0.5 ~ 5h, preferred 0.5 ~ 2h, with reacted material Separation of Solid and Liquid, obtain containing liquid phase material 1 and the remaining solid material 1 of low-carbon alcohols APG;
2) solid material 1 that step 1) is obtained is washed, and the aqueous solution after then will washing obtains liquid phase material 2, i.e. low-carbon alcohols APG solution through concentrated thoroughly dehydration;
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 the low-carbon alcohols APG after merging reaches 20 ~ 95%, and is preferred 50 ~ 60%, obtains liquid phase material 3;
4) in the liquid phase material 3 that step 3) obtains, add the compound that contains the lipophilic group carbochain, add simultaneously catalyst; The compound that contains the lipophilic group carbochain that adds and the mass ratio of the low-carbon alcohols APG in the liquid phase material 3 are 1:1 ~ 1:15, preferred 1:3 ~ 1:5; The addition of catalyst is 0.1% ~ 5%, preferred 0.5% ~ 1.0% of pure low-carbon alcohols glucosides quality; Reaction temperature is 80 ~ 200 ℃, preferred 10 ~ 130 ℃; React under the vacuum, residual voltage is 0.001 ~ 0.05MPa, preferred 0.005 ~ 0.01Mpa; Reaction time is 0.5 ~ 15h, preferred 3 ~ 5h; Neutralization reaction product was to pH=8 ~ 10 after reaction finished;
5) then the product that step 4) the is obtained processing of decolouring adds the long alkyl chain length glucosides solution that water obtains 50% solid content;
6) in the solution that step 5) obtains, add catalyst and pass into air and carry out oxidation reaction; The addition of catalyst is 0.1% ~ 5% of APG quality, preferred 0.5% ~ 1.0%; Reaction temperature is 40 ~ 140 ℃, preferred 60 ~ 90 ℃; Reaction pressure 0.005 ~ 0.03MPa, reaction time 0.5 ~ 10h, preferred 2 ~ 6h keeps pH value of reaction system 2 ~ 10 in the course of reaction, and preferred 4 ~ 6; Obtain containing the product mixed solution of APG carboxylate;
7) in the reacted mixed solution that step 6) obtains, add coupling agent and carry out condensation reaction, make APG and carboxylate derivatives thereof in the 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 the scope, finally obtains surfactant mixture of the present invention.
The described low-carbon alcohols of step 1) can be selected from a kind of in methyl alcohol, ethanol, butanols, ethylene glycol, propane diols or the glycerine, preferred ethylene glycol or propane diols.
The described catalyst of step 1) can be selected from a kind of in p-methyl benzenesulfonic acid, alkyl sulfonic acid, sulfuric acid or the phosphoric acid, preferred p-methyl benzenesulfonic acid.
Step 2) described washing preferred version is: washing times is 1 ~ 8 time, preferred 2 ~ 4 times; Each water consumption is 10% ~ 150 of maize straw quality, preferred 30% ~ 50%; Each washing time is 5 ~ 60 minutes, preferred 10 ~ 40 minutes.
Step 2) aqueous solution after described will the washing is concentrated, is concentrated through the permeable membrane dehydration first, and then carries out decompression distillation and thoroughly dewater.Described reduced pressure distillation process condition comprises: temperature is 50 ~ 160 ℃, preferred 80 ~ 120 ℃; Pressure is 0.01 ~ 0.09Mpa, preferred 0.04 ~ 0.06Mpa.
The described concentrated preferred vacuum distillation method of step 3), vapo(u)rizing temperature is 80 ~ 200 ℃, preferred 110 ~ 140 ℃; Vacuum is residual voltage 0.002 ~ 0.09MPa, preferred 0.01 ~ 0.03Mpa.
The described compound that contains the lipophilic group carbochain of 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, the perhaps ethoxylated product of these materials; The adduct number of the oxirane of the ethoxylated product of described these materials is to be 0 ~ 15, preferred 2-5.
The described catalyst of 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
4Among the-/Ti-La-O any one.
During the described decolouring of step 5) was 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 preferred 3% ~ 6%; Bleaching temperature is 50 ~ 120 ℃, preferred 70 ~ 90 ℃; Bleaching time is 0.1 ~ 3h, preferred 0.5 ~ 1h.
The described solid acid catalyst of 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.
The described coupling agent of 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 two monoxone acid amides of preferred 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 the midbody product APG, and this APG need not separate, and directly carries out next step reaction and synthesizes 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 efficient little, that need not carry out complex separations operation, product improve greatly, product serviceability temperature wide ranges, product to electrolytical tolerance by force, the 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 of the prior art series, AEO are serial, AES, alkyl benzene sulphonate, than 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, as a kind of efficient, environmental protection, infant industry surfactant, has 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.
Below take the surfactant mixture product of the embodiment of the invention 1 preparation as example, prove that product of the present invention compares with existing product and have good performance and effect:
One, activating agent key property test data (seeing Table 1):
Table 1.
| Critical micelle concentration mg/L | Surface tension mN/m | |
| The mixture 1 of embodiment 1 preparation | 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 see Table 2:
Table 2.
2. the performance data of testing under the embodiment of the invention 1 product variable concentrations sees Table 3
Table 3
Three, the performance indications correction data of product of the present invention and prior art products is analyzed:
1, uses as metal cleaner, compare with NPE (NP-10), AEO AEO9, APG, product of the present invention reduces 20 ~ 30% in the situation that add dosage, still can reach same degreasing rate and cleaning performance, and rustless property is obviously good.
2, use as the textile printing and dyeing industry cleaning agent, compare with NPE (NP-10), AEO AEO9, APG, product of the present invention reduces 20 ~ 25% in the situation that add dosage, still can reach same detergency and cleaning performance.
3, be used for civilian liquid detergent, washing powder and public utility cleaning agent (the various cleaning agents such as hotel sheet, the tablecloth, carpet, glass) prescription, good with surfactant compatibilities such as AES, sodium alkyl benzene sulfonate, AEO9, AEC, remarkable liquid detergent cost and reach same or slightly high detergency, hardness better adaptability to water quality, in the high water quality of hardness, have more advantage, and the clothing pliability after washing improves.
The specific embodiment
Embodiment 1
With bale opener with the maize straw Bales Off, the process pulverizer is with corn straw smashing, be transported to storage bin, through transport tape corn stalk powder is transported to 4000kg the 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 of weighing, under 160 ℃ temperature, reacted 1.5 hours; Reacted material is forwarded in the centrifuge, isolate liquid phase material; Change liquid material over to the 1# storage tank stores, then use 800kg, 70 ℃ washing 15 minutes, centrifugal dehydration 10 minutes, the water after washing deposits the 2# storage tank in, repeats this operation and washes altogether 3 times, and is dry through rotary drum dryer through the solid material after the washing, the pack warehouse-in; Concentrated through the permeable membrane dehydration first from the aqueous solution of 2# storage tank after with wash-out, then squeeze into dehydrating kettle (2# still) with pump, under 95 ℃ temperature, the vacuum of-0.03MPa, distillation dehydration 1.5 hours, material after the dehydration distillation is sent into the 1# storage tank, from the 1# storage tank material is squeezed into concentration kettle (3# still) with pump, temperature at 145 ℃, the vacuum of-0.08MPa, distillation was taken off ethylene glycol 2.5 hours, material after concentrated is sent into APG prepare still (4# still), in the 4# still, add palm oil fatty acid list isopropanol amide APEO (ethoxymer distribution is 3) 1200kg, catalyst amber sulfonic acid 10kg is 120 ℃ temperature, under-0.096MPa the vacuum degree condition, reacted 3.5 hours; In the 4# still, add nertralizer magnesia 25kg, stirred 0.5 hour; In the 4# still, drip (dripping off in 30 minutes) decolorizer hydrogen peroxide 80kg, 80 ℃ temperature, reaction 1.5 hours; In the 4# still, add 2400kg water, stirred 0.5 hour, obtain the APG of 50% solid content; The APG of 4# still 50% solid content is transferred to the APG derivative to be prepared in the still (5# still), add catalyst compound solid-acid 22kg, pass into the air of purification in the 5# still by roots blower, temperature at 75 ℃, 0.015MPa under the pressure condition, reacted 5 hours, by setting the numerical value of pH transmission system signal, the sodium hydroxide solution of automatic dripping 30% guarantees that pH value of reaction system is in 4 ~ 6 the scope in the reactor, use the filter filtering recovering catalyst, for reusing later on (reusable 20 ~ 30 times), add the two monoxone acid amides 80kg of coupling agent ethylenediamine, temperature at 85 ° of C, the pH value of reaction system is controlled in 8 ~ 9 the scope, reacted 2 hours, obtain final products---contain the surfactant mixture 1 of 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 R is C in the following formula
15H
31Hydrocarbon chain and the compound of n=4 and following 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 with the maize straw Bales Off, the process pulverizer is with corn straw smashing, be transported to storage bin, through transport tape corn stalk powder is transported to 4000kg the 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 of weighing, under 160 ℃ temperature, reacted 2 hours; Reacted material is forwarded in the centrifuge, isolate liquid phase material, change liquid material over to the 1# storage tank stores, then use 800kg, 70 ℃ washing 15 minutes, centrifugal dehydration 10 minutes, water after washing deposits the 2# storage tank in, repeats this operation and washes altogether 3 times, through the solid material after the washing, dry through rotary drum dryer, the pack warehouse-in; Concentrated through the permeable membrane dehydration first from the aqueous solution of 2# storage tank after with wash-out, then squeeze into dehydrating kettle (2# still) with pump, under the temperature of 90 degree, the vacuum of-0.04MPa, distillation dehydration 1.5 hours, material after the dehydration distillation is sent into the 1# storage tank, from the 1# storage tank material is squeezed into concentration kettle (3# still) with pump, temperature at 145 ℃, the vacuum of-0.08MPa, distillation was taken off ethylene glycol 2.5 hours, material after concentrated is sent into APG prepare still (4# still), in the 4# still, add laurate list isopropanol amide APEO (ethoxymer distribution is 3) 1000kg, catalyst amber sulfonic acid 10kg is 120 ℃ temperature, under-0.096MPa the vacuum degree condition, reacted 3.5 hours; In the 4# still, add nertralizer magnesia 25kg, stirred 0.5 hour; In the 4# still, drip (dripping off in 30 minutes) decolorizer hydrogen peroxide 80kg, 80 ℃ temperature, reaction 1.5 hours; In the 4# still, add 2000kg water, stirred 0.5 hour, obtain the APG of 50% solid content; The APG of 4# still 50% solid content is transferred to the APG derivative to be prepared in the still (5# still), add catalyst compound solid-acid 20kg, pass into the air of purification in the 5# still by roots blower, temperature at 75 ℃, 0.015MPa under the pressure condition, reacted 5 hours, by setting the numerical value of pH transmission system signal, the sodium hydroxide solution of automatic dripping 30% guarantees that pH value of reaction system is in 4 ~ 6 the scope in the reactor, use the filter filtering recovering catalyst, for reusing later on (reusable 20 ~ 30 times), add the two monoxone acid amides 100kg of coupling agent ethylenediamine, temperature at 80 ° of C, the pH value of reaction system is controlled in 8 ~ 9 the scope, reacted 2.5 hours, obtain final products---contain the surfactant mixture 2 of 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%
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 with the maize straw Bales Off, the process pulverizer is with corn straw smashing, be transported to storage bin, through transport tape corn stalk powder is transported to 4000kg the 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 of weighing, under 150 ℃ temperature, reacted 1.5 hours; Reacted material is forwarded in the centrifuge, isolate liquid phase material, change liquid material over to the 1# storage tank stores, then use 600kg, 70 ℃ washing 15 minutes, centrifugal dehydration 10 minutes, water after washing deposits the 2# storage tank in, repeats this operation and washes altogether 3 times, through the solid material after the washing, dry through rotary drum dryer, the pack warehouse-in; Concentrated through the permeable membrane dehydration first from the aqueous solution of 2# storage tank after with wash-out, then squeeze into dehydrating kettle (2# still) with pump, under 95 ℃ temperature, the vacuum of-0.03MPa, distillation dehydration 1.5 hours, material after the dehydration distillation is sent into the 1# storage tank, from the 1# storage tank material is squeezed into concentration kettle (3# still) with pump, temperature at 145 ℃, the vacuum of-0.08MPa, distillation was taken off ethylene glycol 2.5 hours, material after concentrated is sent into APG prepare still (4# still), in the 4# still, add palm oil fatty acid list isopropanol amide APEO (ethoxymer distribution is 4) 1100kg, catalyst amber sulfonic acid 10kg is 120 ℃ temperature, under-0.096MPa the vacuum degree condition, reacted 3.5 hours; In the 4# still, add nertralizer magnesia 25kg, stirred 0.5 hour; In the 4# still, drip (dripping off in 30 minutes) decolorizer hydrogen peroxide 90kg, 90 ℃ temperature, reaction 1.5 hours; In the 4# still, add 2200kg water, stirred 0.5 hour, obtain the APG of 50% solid content; The APG of 4# still 50% solid content is transferred to the APG derivative to be prepared in the still (5# still), add catalyst compound solid-acid 24kg, pass into the air of purification in the 5# still by roots blower, temperature at 75 ℃, 0.02MPa under the pressure condition, reacted 4 hours, by setting the numerical value of pH transmission system signal, the sodium hydroxide solution of automatic dripping 30% guarantees that pH value of reaction system is in 4 ~ 6 the scope in the reactor, use the filter filtering recovering catalyst, for reusing later on (reusable 20 ~ 30 times), add coupling agent ethylene glycol bis chloracetate 110kg, temperature at 75 ° of C, the pH value of reaction system is controlled in 8 ~ 9 the scope, reacted 3 hours, obtain final products---contain the surfactant mixture 3 of 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 R is C in the following formula
15H
31Hydrocarbon chain and the compound of n=5 and following 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%
R and n definition are the same;
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%
Wherein R, R
1, m and n definition is the same,
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%
Wherein R, R
1, m and n definition is the same;
8, other components (inorganic salts, low-carbon alcohols glucosides etc.), 3.8%
9, water, 46.2%
Embodiment 4
With bale opener with the maize straw Bales Off, the process pulverizer is with corn straw smashing, be transported to storage bin, through transport tape corn stalk powder is transported to 4000kg the measuring tank from storage bin, then corn stalk powder is put into low-carbon alcohols glycosylation reaction still (1# still), added the 16500kg propane diols by measuring pump, add the catalyst p-methyl benzenesulfonic acid 28kg of weighing, under 180 ℃ temperature, reacted 1 hour; Reacted material is forwarded in the centrifuge, isolate liquid phase material, change liquid material over to the 1# storage tank stores, then use 800kg, 70 ℃ washing 15 minutes, centrifugal dehydration 10 minutes, water after washing deposits the 2# storage tank in, repeats this operation and washes altogether 3 times, through the solid material after the washing, dry through rotary drum dryer, the pack warehouse-in; Concentrated through the permeable membrane dehydration first from the aqueous solution of 2# storage tank after with wash-out, then squeeze into dehydrating kettle (2# still) with pump, under 95 ℃ temperature, the vacuum of-0.03MPa, distillation dehydration 1.5 hours, material after the dehydration distillation is sent into the 1# storage tank, from the 1# storage tank material is squeezed into concentration kettle (3# still) with pump, temperature at 145 ℃, the vacuum of-0.08MPa, distillation was taken off propane diols 2.5 hours, material after concentrated is sent into APG prepare still (4# still), in the 4# still, add oleic acid single ethanol amide APEO (ethoxymer distribution is 2) 1150kg, catalyst amber sulfonic acid 10kg is 120 ℃ temperature, under-0.092MPa the vacuum degree condition, reacted 3.5 hours; In the 4# still, add nertralizer magnesia 25kg, stirred 0.5 hour; In the 4# still, drip (dripping off in 30 minutes) decolorizer hydrogen peroxide 80kg, 80 ℃ temperature, reaction 1.5 hours; In the 4# still, add 2300kg water, stirred 0.5 hour, obtain the APG of 50% solid content; The APG of 4# still 50% solid content is transferred to the APG derivative to be prepared in the still (5# still), add catalyst compound solid-acid 25kg, pass into the air of purification in the 5# still by roots blower, temperature at 75 ℃, 0.025MPa under the pressure condition, reacted 4.5 hours, by setting the numerical value of pH transmission system signal, the sodium hydroxide solution of automatic dripping 30% guarantees that pH value of reaction system is in 4 ~ 6 the scope in the reactor, use the filter filtering recovering catalyst, for reusing later on (reusable 20 ~ 30 times), add the two monoxone acid amides 130kg of coupling agent ethylenediamine, temperature at 75 ° of C, the pH value of reaction system is controlled in 8 ~ 9 the scope, reacted 3 hours, obtain final products---contain the surfactant mixture 4 of 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%
5, the fatty acid alkanol amides polyoxyethylene ether glucosides dimer (double type surfactant) that structure is following, 6.5%
Wherein R, m and n definition is the same, R
1For
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 with the maize straw Bales Off, the process pulverizer is with corn straw smashing, be transported to storage bin, through transport tape corn stalk powder is transported to 4000kg the 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 of weighing to alkyl sulfonic acid 40kg, under 155 ℃ temperature, reacted 2.5 hours; Reacted material is forwarded in the centrifuge, isolate liquid phase material, change liquid material over to the 1# storage tank stores, then use 700kg, 85 ℃ washing 15 minutes, centrifugal dehydration 10 minutes, water after washing deposits the 2# storage tank in, repeats this operation and washes altogether 3 times, through the solid material after the washing, dry through rotary drum dryer, the pack warehouse-in; Concentrated through the permeable membrane dehydration first from the aqueous solution of 2# storage tank after with wash-out, then squeeze into dehydrating kettle (2# still) with pump, under 85 ℃ temperature, the vacuum of-0.045MPa, distillation dehydration 1.5 hours, material after the dehydration distillation is sent into the 1# storage tank, from the 1# storage tank material is squeezed into concentration kettle (3# still) with pump, temperature at 150 ℃, the vacuum of-0.07MPa, distillation was taken off ethylene glycol 2 hours, material after concentrated is sent into APG prepare still (4# still), in the 4# still, add palm oil fatty acid list isopropanol amide ethoxylate (ethoxymer distribution is 3) 1350kg, catalyst amber sulfonic acid 10kg is 125 ℃ temperature, under-0.096MPa the vacuum degree condition, reacted 3.5 hours; In the 4# still, add nertralizer magnesia 28kg, stirred 0.5 hour; In the 4# still, drip (dripping off in 30 minutes) decolorizer hydrogen peroxide 100kg, 95 ℃ temperature, reaction 1 hour; In the 4# still, add 2700kg water, stirred 0.5 hour, obtain the APG of 50% solid content; The APG of 4# still 50% solid content is transferred to the APG derivative to be prepared in the still (5# still), add catalyst compound solid-acid 32kg, pass into the air of purification in the 5# still by roots blower, at 70 ℃, 0.02MPa under the pressure condition, reacted 4.5 hours, by setting the numerical value of pH transmission system signal, the sodium hydroxide solution of automatic dripping 30% guarantees that pH value of reaction system is in 3.5 ~ 5.5 the scope in the reactor, use the filter filtering recovering catalyst, for reusing later on (reusable 20 ~ 30 times), add the two monoxone acid amides 180kg of coupling agent ethylenediamine, temperature at 90 ° of C, the pH value of reaction system is controlled in 8 ~ 9 the scope, reacted 3 hours, obtain final products---contain the surfactant mixture 5 of double type APG derivative, concrete constituent content is as follows, the compound structure of component 1-2 wherein is identical with embodiment 1 corresponding compound structure, but other are all identical with the embodiment respective components except m=1.6 in the component 3-7 compound structure, 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 mixes dimer, 14.5%
8, other components (inorganic salts, low-carbon alcohols glucosides etc.), 4.9%
9, water, 45.1%
The above is the preferred embodiments of the present invention only, is not limited to the present invention, and 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., all should be included within protection scope of the present invention.
Claims (10)
1. surfactant mixture, it is characterized in that: 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 the fatty acid alkanol amides polyoxyethylene ether glucosides carboxylate.
2. surfactant mixture claimed in claim 1 is characterized in that, described fatty acid alkanol amides polyoxyethylene ether glucosides is that structure is suc as formula the compound shown in (1), wherein, R is the hydrocarbon chain of C11-17, the integer of n=3 ~ 5, and the rational of m=1 ~ 5:
3. surfactant mixture claimed in claim 1 is characterized in that, described fatty acid alkanol amides polyoxyethylene ether glucosides carboxylate is that structure is suc as formula the compound shown in (2), wherein, R is the hydrocarbon chain of C11-17, the integer of n=3 ~ 5, and the rational of m=1 ~ 5:
4. surfactant mixture claimed in claim 1, it is characterized in that, the dimer of any one in described fatty acid alkanol amides polyoxyethylene ether glucosides and the 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.
5. surfactant mixture claimed in claim 4 is characterized in that, described fatty acid alkanol amides polyoxyethylene ether glucosides dimer is structure suc as formula the compound shown in (3):
Wherein, R is the hydrocarbon chain of C11-17;
R
1For
-CH
2-CH
2Or-person;
The integer of n=3 ~ 5, and the rational of m=1 ~ 5.
6. surfactant mixture claimed in claim 4 is characterized in that, described fatty acid alkanol amides polyoxyethylene ether glucosides carboxylate dimer is structure suc as formula the compound shown in (4):
Wherein, R is the hydrocarbon chain of C11-17;
R
1For
-CH
2-CH
2Or-person;
The integer of n=3 ~ 5, and the rational of m=1 ~ 5.
7. surfactant mixture claimed in claim 4, it is characterized in that, described fatty acid alkanol amides polyoxyethylene ether glucosides and fatty acid alkanol amides polyoxyethylene ether glucosides carboxylate to mix dimer be structure suc as formula the compound shown in (5):
Wherein, R is the hydrocarbon chain of C11-17;
R
1For
The person;
The integer of n=3 ~ 5, and the rational of m=1 ~ 5.
8. surfactant mixture claimed in claim 1 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%.
9. surfactant mixture claimed in claim 8 is characterized in that, according to weight percent meter, further contains 4 ~ 10% fatty acid alkanol amides polyoxyethylene and 3 ~ 8% fatty acid alkanol amides polyethenoxy ether carboxylate.
10. method for preparing surfactant mixture claimed in claim 1 may further comprise the steps:
1) in the maize straw of pulverizing, adds low-carbon alcohols and catalyst and carry out the 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, with reacted material Separation of Solid and Liquid, obtain containing liquid phase material 1 and the remaining solid material 1 of low-carbon alcohols APG;
2) solid material 1 that step 1) is obtained is washed, and the aqueous solution after then will washing obtains liquid phase material 2, i.e. low-carbon alcohols APG solution through concentrated thoroughly dehydration;
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 the low-carbon alcohols APG after merging reaches 20 ~ 95%, obtains liquid phase material 3;
4) in the liquid phase material 3 that step 3) obtains, add the compound that contains the lipophilic group carbochain, add simultaneously catalyst; The compound that contains the lipophilic group carbochain that adds and the mass ratio of the low-carbon alcohols APG in the liquid phase material 3 are 1:1 ~ 1:15; The addition of catalyst is 0.1% ~ 5% of pure low-carbon alcohols glucosides quality; Reaction temperature is 80 ~ 200 ℃; React under the vacuum, residual voltage is 0.001 ~ 0.05MPa; Reaction time is 0.5 ~ 15h; Neutralization reaction product was to pH=8 ~ 10 after reaction finished;
5) then the product that step 4) the is obtained processing of decolouring adds the long alkyl chain length glucosides solution that water obtains 50% solid content;
6) in the solution that step 5) obtains, 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 the course of reaction; Obtain containing the product mixed solution of APG carboxylate;
7) in the reacted mixed solution that step 6) obtains, add coupling agent and carry out condensation reaction, make APG and carboxylate derivatives thereof in the 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 the scope, finally obtains described surfactant mixture.
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