CN106543982A - A kind of method for preparing propylene glycol anti-icing fluid from natural wooden fiber's element raw material - Google Patents
A kind of method for preparing propylene glycol anti-icing fluid from natural wooden fiber's element raw material Download PDFInfo
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Abstract
The invention provides a kind of method for preparing propylene glycol anti-icing fluid from natural wooden fiber's element raw material, with lignocellulose biomass such as stalk, corncobs as raw material, in the aqueous solution of paste state bed reactor, the effect of Jing catalyst obtains the aqueous solution product based on propane diols；And change the concentration of aqueous solution of propylene glycol to allocate the propylene glycol anti-icing fluid of environmental protection high-quality by distillation or the method such as UF membrane.The raw material of the present invention is cheap and easy to get, and product value is high, and course of reaction is gentle and transformation efficiency is high；Reacted using discarded biomass, substantially increased the using value of waste wood cellulosic material.
Description
Technical field
Present invention relates particularly to a kind of method for preparing propylene glycol anti-icing fluid from lignocellulosic waste agronomic crop.
Background technology
Continually developing and utilizing with fossil resources such as oil, coal, natural gases, generates the shortage of energy chemistry product and ring
A series of problems, such as border is polluted.And based on environmental protection and the demand of sustainable development, waste agronomic crop is used as sustainable regeneration
Raw material, be easy to get as which is extremely cheap, receive more and more attention and study.Abandoned biomass includes agriculture life
The discarded object for producing and the plant such as residue, forest and forestry processing waste, careless class, are most abundant renewable on the earth
Resource, which is mainly made up of lignin, cellulose and three part of hemicellulose.In the discarded plant of various separate sources, one
As cellulose account for 40-60%, lignin accounts for 20-30%, and hemicellulose accounts for 10-40%.
China is large agricultural country, and stalk biomass has yield big (more than 700,000,000 tons), source extensively (mainly to have water in China
Rice, wheat and maize straw etc.), biological raw material lower-price characteristic.Stalk because can be used for farmland also field containing N, P, K, but
Due to the raising and exploitation of fertilizer technology, stalk is used for the quantity in also field and die-offs.And substantial amounts of crop straw burning causes haze
One of arch-criminal.Therefore, the effectively utilizes for developing stalk have huge social effect and economic benefit.Master of the cellulose for stalk
Composition, obtains the dihydroxylic alcohols such as ethylene glycol, propane diols with very high economy and using value by raw material Efficient Conversion of stalk.
Some reports that dihydroxylic alcohols is converted into regard to cellulose catalytic are had, Chinese patent CN 1017350114B are disclosed
A kind of method of preparing ethanediol from polyhydroxy compounds, there is provided it is a kind of by polyol (include starch, hemicellulose,
Sucrose, glucose, fructose, levulan) method for preparing ethylene glycol.The method with polyol as reaction raw materials, with 8,
9th, 10 group 4 transition metal iron, cobalt, nickel, ruthenium, rhodium, palladium, platinum and molybdenum, the Titanium of tungsten, carbide, nitride, phosphide are catalysis
Active component constitutes multimetal reforming catalyst, at 120-300 DEG C, through a step catalyzed conversion under conditions of Hydrogen Vapor Pressure 1-13MPa
Process, realizes polyol efficiently and high selectivity, prepares ethylene glycol in high yield.
Chinese patent CN 101723802B disclose a kind of method of preparing ethylene glycol from cellulose, and the method with cellulose is
Reaction raw materials, with 8,9,10 group 4 transition metal iron, cobalt, nickel, ruthenium, rhodium, palladium, platinum and molybdenum, the Titanium of tungsten, carbide, nitride,
Phosphide is that catalytic active component constitutes multimetal reforming catalyst, at 120-300 DEG C, under the hydrothermal condition of Hydrogen Vapor Pressure 1-12MPa
Realize that cellulose prepares the process of ethylene glycol through a step catalyzed conversion.
The patent that dihydroxylic alcohols is generated using original biomass such as stalk also includes：Chinese patent CN 103667365A are public
A kind of method that agricultural crop straw prepares dihydroxylic alcohols is opened.The disclosure of the invention one kind carries out diluted acid leaching by raw material of agricultural crop straw
Stain, Jing short time high temperatures pre-process the refinement treatment systems such as Jing cellulose hydrolyzations again, decolorization filtering, ion exchange, efficient concentration
Obtain stalk sugar.Subsequently under nickel alloy catalyst effect, the continuous high-pressure hydrogenation cracking of Jing obtains dihydroxylic alcohols and polyalcohol to stalk sugar
Mixture, the pyrolysis product product such as the isolated ethylene glycol of Jing rectifications under vacuum and propane diols again.
Chinese patent CN 1915947A disclose a kind of method that utilization string produces polyalcohol, and this invention passes through
The steps such as hydrolysis, hydrogenation, hydrogenolysis, separation, and various technological parameters needed for adjusting, obtain various single components
Polyalcohol.
Generally, cellulose just can be decomposed with achievement unit by the hydrogen ion for ionizing out in high-temperature water in water
Poly-, there is inverse Alder reaction fracture C-C key lifes in water power in the glucose that cellulose hydrolysis is generated under hydrionic effect
Into ethylene glycol.The reaction efficiency for directly preparing dihydroxylic alcohols using Crop transformation is general all very low, and the product complicated difficult for obtaining
Separate, thus the separating step of the complicated power consumption of multistep is needed to obtain pure dihydroxylic alcohols final products.
Mainly based on the anti-icing fluid rich in ethylene glycol, but ethylene glycol is toxic, its metabolite for present domestic market
Toxicity for glycolaldehyde, glycolic and glyoxylic acid is relatively large, it is easy to cause to eat by mistake and be poisoned.
The content of the invention
The invention aims to solve the deficiencies in the prior art, there is provided a kind of from natural wooden fiber's element raw material element system
The method of standby propylene glycol anti-icing fluid, it is characterised in that include：
Step 1, the pretreatment of natural wooden fiber's element raw material：
Natural wooden fiber's element raw material is added in inorganic alkali solution, inorganic alkali solution is heated to 60～100 DEG C, in nothing
10～80h is heated to natural wooden fiber's element raw material in machine aqueous slkali；
Natural wooden fiber's element raw material after heating in inorganic alkali solution is added in organic alkali solution, and heating has
Machine aqueous slkali heats 60～120h to natural wooden fiber's element raw material to 80～100 DEG C in organic alkali solution；
Step 2, prepares catalyst：
The salt of Ru or/and Pt is dissolved in deionized water, the salt of carrier and auxiliary agent is added, normal temperature rotary evaporation is until anhydrous
Afterwards, it is dried in being placed on vacuum drying chamber；Dried solid is added in reactor, carries out reducing instead with the hydrogen being passed through
Should, the temperature of reduction is 300～600 DEG C, and the recovery time is 2～6h, obtains catalyst；The catalyst for obtaining includes activity
Component, auxiliary agent and carrier, the main active component are Ru or/and Pt, and the quality of the active component is catalyst quality
0.1-10%；
Step 3, after the natural wooden fiber's element raw material after heating is mixed with water, is added to slurry bed system in step 1
In reactor, while obtaining catalyst in adding step 2；The water is 100 with the weight ratio of natural wooden fiber's element raw material：1-
100：80, the quality of the catalyst is the 0.1～0.5% of the quality of natural wooden fiber's element raw material；
Step 4, is passed through hydrogen in paste state bed reactor, replaces three nitrogen, under catalyst action, the natural wood
Matter cellulosic material direct hydrogenation is cracked into the mixed solution based on propane diols；Reaction temperature is 100～300 DEG C, hydrogen pressure
Power is 3.0～10.0MPa, and the reaction time is 0.5～5h；
Step 5, is processed by distillation, after the mixed solution for obtaining is concentrated, adds triethanolamine, sweet in step 4
Propylhomoserin, BTA, orchil, are prepared into propylene glycol anti-icing fluid.
Above-mentioned method, wherein, in the step 1, natural wooden fiber's element raw material is selected from stalk, wood chip, corn
One or more in core, birch, poplar, maple, pine, dragon spruce.
Above-mentioned method, wherein, in the step 1, the inorganic alkali solution is selected from NaOH, KOH, Ca (OH)2、NH3·
H2One or more in O.
Above-mentioned method, wherein, in the step 1, the one kind or two of the organic alkali solution in triethylamine, pyridine
Kind.
Above-mentioned method, wherein, in the step 2, the auxiliary agent in the catalyst selected from Ni, Fe, Co, Pd, Au, Mo,
One or more in Sn, Cu, Zr, Ir, La, the quality of the auxiliary agent is the 0.01～2% of catalyst quality.
By adding auxiliary agent in the catalyst, thus it is possible to vary the electronic state of active component Ru or/and Pt, especially electricity is negative
Proterties state.The auxiliary agent of addition can make active component more electron deficient, strengthen the ability that active component hydrogenolysis activates C-O and C-C keys,
The efficiency of catalyst is greatly improved.The auxiliary agent of increase is it is also possible that the metallic particles of active component Ru or/and Pt is less
And disperse evenly, to be also beneficial to improve the efficiency of catalyst.
Above-mentioned method, wherein, in the step 2, the carrier in the catalyst is hydrostable high-area carbon or oxygen
Compound carrier.Preferably, the carrier is activated carbon or Graphene.
Heterogeneous catalytic reaction is carried out on the metal active site of surface of solid phase carriers, and suitable carrier especially compares table
High, stable under the reaction environment carrier of area, the decentralization to improving metal have very big help.High-area carbon and oxidation
Thing carrier has higher specific surface area, and relatively stable to the water environment of hyperpyrexia.
Above-mentioned method, wherein, in the step 3, the quality of the catalyst is the matter of natural wooden fiber's element raw material
The 0.1～0.2% of amount.
Above-mentioned method, wherein, in the step 4, reaction temperature be 150～250 DEG C, Hydrogen Vapor Pressure be 3.0MPa～
6.0MPa。
Above-mentioned method, wherein, in the step 5, in the propylene glycol anti-icing fluid, the quality of propane diols accounts for the third two
The 50～70% of alcohol type anti-icing fluid gross mass.
In the present invention, natural wooden fiber's element raw material is effectively hydrolyzed to by glucose sugar by pretreatment first, is generated
Glucose sugar be isomerized to fructose under catalyst action, there is inverse Alder reaction fracture C-C keys and generate 1,3- dihydroxies in fructose
Benzylacetone and 2,3- dihydroxy propionic aldehyde；Last both products generate propane diols Jing after being dehydrated and be hydrogenated with.
The metal nanoparticle centrophyten very little being supported on high-area carbon, with very high specific surface energy and more exposures
High energy crystal face, thus under gentle reaction condition activity it is very high.In catalyst, highly active active component can make natural wood
Matter cellulosic material flash hydrogcnation generates intermediate product, and quick from intermediate product generation propane diols.For the rate determining step of reaction
The inverse Alder reaction of rapid i.e. fructose, the auxiliary agent of addition can be obviously promoted the ionization of water, and then make hydrogen ion concentration increase quickening
The speed of fracture C-C keys, it is often more important that the auxiliary agent being introduced into can cause No. 3 into complex compound with the bond symphysis of the C-C in fructose
Position C-C keys it is elongated so as to be more beneficial for occur C-C cleavage reactions.Due to the soda acid function that the auxiliary agent for introducing shows, this is made
It is obvious to have taken off the acid or the use of alkali for being unfavorable for environment, really realize overall process greenization, environmental protection.
In sum, compared with prior art, the invention has the advantages that and beneficial effect：
(1) transformation efficiency height of the present invention, reaction condition temperature, and energy consumption is low, is comprehensively and effectively to utilize lignocellulose
Abandoned biomass resource provides approach, orients conversion with really realizing Atom economy.Various two are being converted into especially
First alcohol makes full use of the effect of catalyst so that glucose sugar tautomerizes to fructose, and then causes to generate product for more during this
The ethylene glycol of the propane diols rather than routine of high value.
(2) present invention is raw material using discarded lignocellulose-like biomass resource, is produced by Non oil-based route
Propane diols anti-icing fluid.Preparation process is simple and convenient, and the anti-icing fluid Product Green rich in propane diols for obtaining is environmentally friendly, pollution-free, nothing
Toxicity, anticorrosive, degradable, performance is suitable with ethylene glycol type anti-icing fluid；And price is high, improves the economic worth of anti-icing fluid.
(3) active component Ru and Pt in catalyst of the present invention, compare during preparation other metals such as Fe,
Co, Ni etc. easily prepare the smaller particle of particle diameter.Changed using auxiliary agent main activated centre electronegativity and decentralization and
The ability of its further chain rupture C-C key and C-O keys, and carried using the charcoal with high-specific surface area and hydrothermal stability and oxide
Body realizes the high efficiency of catalyst.
(4) present invention directly realizes the conversion of biomass macromolecular in pure water phase solvent, using the nanocrystalline height of multiphase
Crystal face activity is fully contacted with the avtive spot of cellulose to realize efficient catalytic reaction, has advantageously been broken away from course of reaction
The pollution of acid or the use of alkali to environment, veritably realizes the greenization of overall process.
(5) main component of present invention gained is propylene glycol solution, without the need for follow-up complex separations step, by simple
Water separates the propylene glycol motor vehicle antifreeze fluid that concentration can be prepared into high-quality and environmental protection, and the simple and environmentally-friendly green of process is fitted
Close large-scale production and high financial profit.
Specific embodiment
Embodiment 1,
The pretreatment of natural wooden fiber's element raw material：
Stalk is added in NaOH solution, heating NaOH solution heats to stalk in NaOH solution to 80 DEG C
10～80h.Stalk after heating in NaOH solution is added in triethylamine solution, triethylamine solution is heated to 90 DEG C,
100h is heated to stalk in triethylamine solution.
Embodiment 2
Weigh 2g platinum tetrachlorides to be dissolved in the deionized water of 50ml, the absorbent charcoal carrier for adding dry coconut husk to prepare,
Nickel nitrate is added simultaneously, and normal temperature rotary evaporation is until after anhydrous, be dried in being placed on vacuum drying chamber.Dried solid is added
Entering in reactor, reduction reaction being carried out with the hydrogen being passed through, reduction temperature is 350 DEG C, and the recovery time is 4h, obtains catalyst
Pt-Ni/C (coconut husk).
Embodiment 3
After by the water mixing of 40g pretreated stalk and 100ml, it is added in paste state bed reactor, while adding
0.5g catalyst Pt-Ni/C (Graphene), and it is passed through 3MPa hydrogen；After being heated to 240 DEG C, reaction 1h is maintained, three nitrogen are replaced
Gas, speed of agitator are 650rpm, obtain the mixed solution based on propane diols；After mixed solution is cooled to room temperature, stop stirring,
Discharge gas.
Embodiment 4
40g pretreated stalk is reacted using different catalyst, other conditions are same as Example 3.
Taking reacted mixed solution sample carries out GC-MS analyses, as a result as shown in table 1：
Table 1
When as can be known from the results of Table 1, using catalyst Pt-Ni/C (Graphene), water transfer cellulose efficiency most
It is high.
Embodiment 5
Different lignocellulose waste biomass materials are reacted using catalyst Pt-Ni/C (Graphene),
Other conditions are same as Example 3.Lignocellulose waste biomass materials include cypress bits, poplar, birch, wheat
Bar, paddy rice bar.
Reaction result is as shown in table 2：
Table 2
By the result of table 2, growth year short plant such as rice straw conversion ratio is higher, and this is likely due to plant
Thing is with the spontaneous structure all the more close and firm of growth of growth year, it is not easy to the reason for contacting activated centre and react.
Embodiment described above is merely to illustrate the technological thought and feature of the present invention, its object is to make in the art
Technical staff will appreciate that present disclosure and implement according to this, it is impossible to limit only with the present embodiment the present invention patent model
Enclose, i.e., all equal changes made according to disclosed spirit or modification, still fall in the scope of the claims of the present invention.
Claims (9)
1. it is a kind of from natural wooden fiber's element raw material method for preparing propylene glycol anti-icing fluid, it is characterised in that to include：
Step 1, the pretreatment of natural wooden fiber's element raw material：
Natural wooden fiber's element raw material is added in inorganic alkali solution, inorganic alkali solution is heated to 60～100 DEG C, in inorganic base
10～80h is heated to natural wooden fiber's element raw material in solution；
Natural wooden fiber's element raw material after heating in inorganic alkali solution is added in organic alkali solution, heats organic base
Solution heats 60～120h to natural wooden fiber's element raw material to 80～100 DEG C in organic alkali solution；
Step 2, prepares catalyst：
The salt of Ru or/and Pt is dissolved in deionized water, the salt of carrier and auxiliary agent is added, normal temperature rotary evaporation until after anhydrous,
It is dried in being placed on vacuum drying chamber；Dried solid is added in reactor, reduction reaction is carried out with the hydrogen being passed through, also
Former temperature is 300～600 DEG C, and the recovery time is 2～6h, obtains catalyst；The catalyst for obtaining include active component,
Auxiliary agent and carrier, the main active component are Ru or/and Pt, and the quality of the active component is the 0.1- of catalyst quality
10%；
Step 3, after the natural wooden fiber's element raw material after heating is mixed with water, is added to slurry reactor in step 1
In device, while obtaining catalyst in adding step 2；The water is 100 with the weight ratio of natural wooden fiber's element raw material：1-100：
80, the quality of the catalyst is the 0.1～0.5% of the quality of natural wooden fiber's element raw material；
Step 4, is passed through hydrogen in paste state bed reactor, replaces three nitrogen, and under catalyst action, the natural wood is fine
The plain raw material direct hydrogenation of dimension is cracked into the mixed solution based on propane diols；Reaction temperature is 100～300 DEG C, and Hydrogen Vapor Pressure is
3.0～10.0MPa, reaction time are 0.5～5h；
Step 5, by distillation process, after the mixed solution obtained in step 4 is concentrated, add triethanolamine, glycine,
BTA, orchil, are prepared into propylene glycol anti-icing fluid.
2. method according to claim 1, it is characterised in that in the step 1, natural wooden fiber's element raw material choosing
One or more from stalk, wood chip, corncob, birch, poplar, maple, pine, dragon spruce.
3. method according to claim 1, it is characterised in that in the step 1, the inorganic alkali solution selected from NaOH,
KOH、Ca(OH)2、NH3·H2One or more in O.
4. method according to claim 1, it is characterised in that in the step 1, the organic alkali solution are selected from three second
One or two in amine, pyridine.
5. method according to claim 1, it is characterised in that in the step 2, the auxiliary agent in the catalyst is selected from
One or more in Ni, Fe, Co, Pd, Au, Mo, Sn, Cu, Zr, Ir, La, the quality of the auxiliary agent is catalyst quality
0.01～2%.
6. method according to claim 1, it is characterised in that in the step 2, the carrier in the catalyst is to water
Stable high-area carbon or oxide carrier.
7. method according to claim 1, it is characterised in that in the step 3, the quality of the catalyst is natural wood
The 0.1～0.2% of the quality of matter cellulosic material.
8. method according to claim 1, it is characterised in that in the step 4, reaction temperature are 150～250 DEG C, hydrogen
Atmospheric pressure is 3.0MPa～6.0MPa.
9. method according to claim 1, it is characterised in that in the step 5, in the propylene glycol anti-icing fluid,
The quality of propane diols accounts for the 50～70% of propylene glycol anti-icing fluid gross mass.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113563853A (en) * | 2021-07-26 | 2021-10-29 | 中国石油化工股份有限公司 | Environment-friendly cooling liquid composition and application thereof |
| CN113773814A (en) * | 2021-09-24 | 2021-12-10 | 长春工业大学 | Preparation method of bio-based anti-freezing agent |
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