CN108949264A - It is a kind of efficiently to purify straw base diesel fuel additives and preparation method thereof - Google Patents

It is a kind of efficiently to purify straw base diesel fuel additives and preparation method thereof Download PDF

Info

Publication number
CN108949264A
CN108949264A CN201810714814.XA CN201810714814A CN108949264A CN 108949264 A CN108949264 A CN 108949264A CN 201810714814 A CN201810714814 A CN 201810714814A CN 108949264 A CN108949264 A CN 108949264A
Authority
CN
China
Prior art keywords
straw
filtrate
fraction
straw powder
alcoholysis
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201810714814.XA
Other languages
Chinese (zh)
Inventor
曹大强
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
SUNACORE NEW ENERGY CO Ltd
Original Assignee
SUNACORE NEW ENERGY CO Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by SUNACORE NEW ENERGY CO Ltd filed Critical SUNACORE NEW ENERGY CO Ltd
Priority to CN201810714814.XA priority Critical patent/CN108949264A/en
Publication of CN108949264A publication Critical patent/CN108949264A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/1817—Compounds of uncertain formula; reaction products where mixtures of compounds are obtained
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2230/00—Function and purpose of a components of a fuel or the composition as a whole
    • C10L2230/22—Function and purpose of a components of a fuel or the composition as a whole for improving fuel economy or fuel efficiency
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2270/00—Specifically adapted fuels
    • C10L2270/02—Specifically adapted fuels for internal combustion engines
    • C10L2270/026—Specifically adapted fuels for internal combustion engines for diesel engines, e.g. automobiles, stationary, marine

Abstract

The invention discloses a kind of efficiently purification straw base diesel fuel additives, including corn stover alcoholysis to product, the obtained mixing of product of straminol solution.Corn stover alcoholysis to product and the obtained mixing mass ratio of product of straminol solution be 1~2:1~5.The invention also discloses a kind of methods for preparing above-mentioned straw base diesel fuel additives.The present invention has the advantages of fractional distillation purifies to obtain the more pure diesel fuel additives based on ethyl levulinate ingredient, improves the efficiency of combustion of diesel oil.

Description

It is a kind of efficiently to purify straw base diesel fuel additives and preparation method thereof
Technical field
The present invention relates to the evaluation and exploration technology fields of new energy, more particularly to a kind of efficiently purification straw base diesel oil addition Agent and preparation method thereof.
Background technique
Ethyl levulinate contains a carbonyl as a kind of potential green bio matter based platform compound in molecule With an ester group, there is good reactivity, be able to carry out hydrolysis, reduction, condensation, a variety of reactions of affine addition.It is more than utilization Characteristic, ethyl levulinate is not only applicable to the industries such as solvent, fragrance, oil dope and plasticizer, also as important doctor Medicine and industrial chemicals are widely used in petroleum and replace in addition, ethyl levulinate or a kind of novel liquid fuel additive For energy field.Under acid catalysis, cellulose can degrade first generates glucose glucose and ethyl alcohol in the height of inorganic acid The lower dehydration of temperature catalysis forms Ethyl-glucoside, is further converted to ethoxyl methyl furfural, ethoxyl methyl furfural alcoholysis is Ethyl levulinate and Ethyl formate.
For corn as China staple crops, plantation amount is very big, and the amount of the corn stover of association is also considerable therewith. It is estimated that the corn stover that China generates every year is more than 200,000,000 t, and since the utilization rates such as deep processing are low, wherein most corn stover By burning disposal, environment is produced and is seriously affected.It is well known that corn stover is mainly by cellulose, hemicellulose and wood Quality composition, and these ingredients have significant application value in many fields.
It is well known that wheat stalk is mainly made of cellulose, hemicellulose and lignin, and these ingredients are in many necks There is significant application value in domain.Method for specifically producing methyl ester levulinate, provided temperature condition, pressure strip The conditions such as part, solid-to-liquid ratio all difference, the preparation of methyl ester levulinate is used for for directly refining stalk, certainly with institute Harvest, but for lignin, cellulose and hemicellulose, the condition that catalysis generates methyl ester levulinate is different, as The production highest cellulose of methyl ester levulinate efficiency at present, the lignin and hemicellulose being incorporated in around cellulosic molecule, then The alcoholysis that can hinder cellulose is influenced for how much yield exists, and the by-product of generation will become more to be difficult to locate than stalk The waste of reason, reduces waste to the greatest extent, improves the biomass alcoholysis production methyl ester levulinate of stalk, mentions according to single Take adjusting obvious unreasonable.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of efficiently purification straw base diesel fuel additives and its preparations Method.
The present invention is realized by following technological means solves above-mentioned technical problem: efficiently purification straw base diesel oil adds one kind Add agent, the additive include corn stover alcoholysis to product and the obtained mixing of product of straminol solution.
Preferably: the corn stover alcoholysis to product and the obtained mixing mass ratio of product of straminol solution be 1 ~2:1~5.
Invention additionally discloses a kind of methods for preparing above-mentioned efficient purification straw base diesel fuel additives, wherein the jade Rice stalk alcoholysis to product preparation method the following steps are included: straw powder I is obtained to the pretreatment of corn stover, by straw Stalk powder I carries out delignification and handles to obtain filtrate I and straw powder II, and straw powder II is mixed with ethanol solution, stirs into suspension And the catalyst concentrated sulfuric acid is added, it is transferred to alcoholysis in autoclave, suction filtration obtains filtrate II, distilled to obtain to filtrate II Layering goes to inhale the product arrived that layer solution is prepared corn stover alcoholysis after fraction III, gained fraction III are stood；It is described For the product preparation method that straminol solution obtains the following steps are included: wheat stalk is cleaned, drying obtains straw powder after crushing I, mixed nitrate and ethyl alcohol are configured to reagent, and straw powder I is added into reagent, is filtered after reaction, obtain residue I and molten There are the filtrate I of lignin, filtrate I to be reused after being handled, incites somebody to action to obtain straw powder II；Straw powder II is anti-in sig water It answers, obtains residual II and the filtrate II dissolved with hemicellulose, filtrate II is reused after being handled, residual II is washed It washs, obtains straw powder III；Straw powder III is added to H2O2Solution, after reaction, obtain filtrate II I, filter, washing, dry stalk Powder IV；Straw powder IV is reacted with methanol solution, filters to obtain filtrate IV；Filtrate IV is distilled, fraction, is fraction I, then Fraction I is evaporated under reduced pressure, fraction II is obtained, fraction II is finally collected into fraction in vacuum distillation, is fraction III, gained evaporates Dividing III is the product that straminol solution obtains.
Preferably: the straw powder I carries out the process of delignification processing, first by 1:2~3 volume ratio mixed nitrate and Ethyl alcohol is configured to reagent, and then straw powder I is added into reagent by the solid-to-liquid ratio of 1:12~16, reaction kettle I is transferred to, in temperature 70~90 DEG C of degree reacts 150~200min, is filtered after the reaction was completed, obtain residue I and dissolved with lignin under condition of normal pressure Filtrate I, filtrate I reused after being handled, and is done in 90~105 DEG C of baking ovens after residue I is washed with distilled water Dry 20~30h is spare, obtains straw powder II；
Preferably: the corn stover alcoholysis to product in alcoholysis condition be reaction kettle is heated to it is preset 170~200 DEG C, pressure is 2.00~2.25MPa in kettle, keeps 60~70min at this temperature.
Preferably: the corn stover alcoholysis to product preparation method described in the process of distillation be to take filtrate II It distills under normal pressure, collects the fraction before 80 DEG C, be denoted as fraction I, be then evaporated under reduced pressure, 80~120 DEG C of collection evaporates Point, it is denoted as fraction II, a certain amount of dodecane is added in fraction II, then continues to be evaporated under reduced pressure under the conditions of 120~160 DEG C Gained fraction is collected, fraction III is denoted as.
Preferably: wheat stalk being cleaned, drying smashes it through 60~80 meshes, straw powder I is obtained, by 1:2~3 Volume ratio mixed nitrate and ethyl alcohol be configured to reagent, straw powder I is added by the solid-to-liquid ratio of 1:12~16 into reagent, shift 150~200min is reacted under condition of normal pressure, is filtered, is obtained residual after the reaction was completed at 70~90 DEG C of temperature to reaction kettle I Slag I and filtrate I dissolved with lignin, filtrate I is reused after being handled, in 90 after residue I is washed with distilled water It is dried for standby in~105 DEG C of baking ovens, obtains straw powder II；
Preferably: the NaOH that configuration quality score is 3~6% in the product preparation method that the straminol solution obtains is water-soluble Liquid is added into reaction kettle II, and straw powder II is added in the ratio of solid-to-liquid ratio 1:30~40, stirs into suspension, temperature is arranged 90~110 DEG C of section, 2~3h of boiling are filtered after the completion, obtain residual II and the filtrate II dissolved with hemicellulose, filtrate II is reused after being handled, and is dried for standby in 90~105 DEG C of baking ovens after residual II is washed with distilled water, is obtained straw Stalk powder III；
Preferably: the H that configuration concentration is 2~4% in the product preparation method that the straminol solution obtains2O2Solution, add Enter into reaction kettle III, straw powder III is added in the ratio of solid-to-liquid ratio 1:30~35, stands 5~6h of reaction, must filter after the completion Liquid III filters filtrate II I, washing, dry straw powder IV；
Preferably: by straw powder IV and methanol solution by 1:20~30 in the product preparation method that the straminol solution obtains Mass ratio the concentrated sulfuric acid that its total amount 0.3~0.6% is added to autoclave IV and catalyst Patent alum is added 1~3%, after mixing evenly, sealing, using microwave heating, 800~1000W of microwave power is warming up to 160~180 in 2min DEG C, it is pressurized 2~3MPa, 50~70min of insulation reaction, filters to obtain filtrate IV.
Corn stover alcoholysis stage: the present invention by without slough lignin corn stalk powder carry out alcoholysis, The process of alcoholysis, Step By Condition are identical as step of the invention, then detect the infrared spectrum analysis discovery in alcoholysis liquid, 3383cm in extracting solution-1And 2920cm-1The absorption peak at place be respectively belonging in cellulose-OH and-CH3Group O-H and The stretching vibration of C-H, 1734cm-1Place is the stretching vibration peak of C=O, is the characteristic peak of carbonyl in hemicellulose, 897cm-1It inhales Receive the asymmetric faces external extension and-CH that peak is ring-type C-O-C in cellulose2(CH2OH) the wagging vibration of group, this A little absorption peaks obviously weaken in residue, while 897cm-1The absorption peak at place disappears, it was demonstrated that cellulose and hemicellulose were liquefying Degradation and Transformation has occurred in journey, and C-O-C of the skeleton in lignin is in 1032cm-1The absorption peak at place enhances, then illustrates wood Micro degradation only occurs in liquefaction process for quality, and xylonic acid is not engaged in during being converted into ethyl levulinate, together When due to lignin presence, may be due to the function influence cellulose of barrier and the degradation of hemicellulose.In residue obtained Remaining more lignin.
It is well known that corn stover is since stalk needs certain support performance, content of lignin relative to rice and The proportion of wheat, shared biomass total amount is relatively high, and successively the present invention is when carrying out corn stalk powder alcoholysis to wooden Element has done corresponding removal, by observing the straw powder I particle except delignification, untreated stalk particle, Its surface is comparatively dense smooth, can be obvious without apparent fold and particulate material, and after the step of passing through delignification Find out and ruptured under the particle microexamination of straw powder II, has the formation of partial mesh topology, show in pretreated process In, lignin is destroyed, therefore apparent pit occurs in the position of lignin, and solvent and catalyst can be entered preferably In the internal structure of stalk particle, the component in stalk is degraded.
In straw alcoholysis stage: since the property of nitric acid is relatively mild, the nitro cation NO2 that is generated in reaction dissolvent + and nitroso ion NO+ can with the structural unit of phenolic in lignin and non-phenolic occur phenyl ring on substitution reaction, make wooden Plain molecular hydrophylic improves, and then improves its solvability.
By examination of infrared spectrum products therefrom respectively in lignin, the characteristic peak of hemicellulose and cellulose wavelength period, Detect the characteristic peak of finished product microcrystalline cellulose as a comparison simultaneously, it was therefore concluded that: the main official of cellulose infrared spectroscopy purified Energy group-OH, the symmetric and anti-symmetric absorption peak position of methyl are very close, it was demonstrated that in product based on cellulose, purity is extremely Reach 90% or more less, also shows that in wave number be 1505 in the infrared absorption peak spectrogram of testing result-1The lignin characteristic peak of cm It is 1045 with wave number-1The hemicellulose character peak of cm does not occur, illustrates after being milled to straw, lignin and hemicellulose therein Removal it is more complete.
For extracting cellulose generated secondary treatment reagent in the process, secondary treatment reagent is processing purification for the first time The product of reagent can be used to carry out duplicate production again, can greatly improve the saving to reagent after purification, Wherein simply example is exactly that can be recycled to ethyl alcohol using distillation, even if the effect of purification is not achieved in other reagents Fruit, but still may be reused, the extraction final result of cellulose is influenced it is smaller, have no idea by secondary reality into In the case that row extracts recycling, reagent selected by the present invention compares mostly to be easy to get, inexpensively.
In the alcoholysis process of biomass, catalyst is the key factor for realizing Efficient Conversion, in current multiple catalysts In the case where, there are inorganic acid, solid acid, ionic liquid etc.；These are all conducive to the synthesis of methyl ester levulinate, due to liquid acid It in the presence of the risk of corrosion equipment, is not easily recycled simultaneously, the present invention uses Al2(SO4)3·18H2O is as catalyst, Al2 (SO4)3·18H2O has preferable catalytic activity, fresh Al2(SO4)3·18H2O particle has different crystal habit and ruler It is very little, and a degree of reunion is showed, but can be seen that urging for recycling from the scanning electron microscope (SEM) photograph of 5 rear catalysts of reaction Agent particle compared with fresh significantly increases, and agglomeration is obvious.And the catalyst color after reacting becomes ash by white White, caused by this may be catalyst surface carbon distribution；But recycling Al2(SO4)3·18H2O catalyst still has Good activity characteristic compares fresh Al2(SO4)3·18H2O solid catalyst, the influence for methyl ester levulinate yield is only 5% or so, therefore be the catalyst that may be reused.
Recycling for solid catalyst is one of the important indicator for investigating catalyst economics, on the basis of optimization technique On, the catalyst after reaction can be recycled, obtained solid, which is added in fresh reaction system, to be carried out repeating reaction, sulphur Sour aluminium can be repeated several times for catalytic process, and just have preferable effect.
The present invention has the advantages that
(1) by removing the lignin in stalk by chemical method, leading to remaining straw before corn stover alcoholysis There is extensive netted pore in stalk powder surface, and one side xylonic acid is not the raw material for converting ethyl levulinate, on the other hand, The presence of xylonic acid hinders the alcoholysis of cellulose and hemicellulose, and last fractional distillation purifies to obtain more pure with levulinic Diesel fuel additives based on acetoacetic ester ingredient improves the efficiency of combustion of diesel oil.
(2) yield for improving methyl ester levulinate solves agricultural by-products to stalk using new understanding is proposed Reluctant problem, the present invention be emphasized that this efficient side using extraction of levulinic acid methyl esters to stalk for many years Method is not limited only to straw, is equally applicable to corn stover, rice straw, sesame stalk etc., the stalk high for content of cellulose, Better economic benefit will be had.
Methyl ester levulinate is generated for stalk to be catalyzed, it is first to carry out to stalk that the present invention, which has better method, The main matter cellulose for extracting production methyl ester levulinate is concentrated in more stringent pretreatment, for rejecting lignin, half The by-product relatively of the invention such as cellulose, it will as other substances are produced, as field of papermaking, field of textiles do emphasis benefit With being utilized to the layering of stalk, improve the highest economic benefit of stalk, also have simultaneously for target product methyl ester levulinate Better yield.
Specific embodiment
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in the embodiment of the present invention Technical solution is clearly and completely described, it is clear that described embodiments are some of the embodiments of the present invention, rather than complete The embodiment in portion.Based on the embodiments of the present invention, those of ordinary skill in the art are without creative efforts Every other embodiment obtained, shall fall within the protection scope of the present invention.
Embodiment 1:
The present embodiment discloses a kind of method that corn stover prepares diesel fuel additives, including following steps,
(1) corn stover is cleaned, drying smashes it through 70 meshes, obtains straw powder I, mixes by the volume ratio of 1:2 Nitric acid and ethyl alcohol are configured to reagent, and straw powder I is added by the solid-to-liquid ratio of 1:14 into reagent, reaction kettle I is transferred to, in temperature , 180min is reacted under condition of normal pressure, is filtered after the reaction was completed, obtains residue I and the filtrate I dissolved with lignin, filter by 80 DEG C Liquid I is reused after being handled, and dry 25h is spare in 95 DEG C of baking ovens after residue I is washed with distilled water, and obtains stalk Powder II；
(2) straw powder II is mixed in the ratio of solid-to-liquid ratio 1:15 with ethanol solution, stirs into suspension, it is then more mixed The catalyst concentrated sulfuric acid is added to concentrated sulfuric acid concentration 2wt% in the total amount for closing liquid, is transferred in autoclave after mixing, sealing reaction Reaction kettle is heated to preset 180 DEG C by kettle, and pressure is 2.25MPa in kettle, is kept 65min at this temperature, is filtered after complete vehicle Obtain filtrate II；
(3) it takes filtrate II to distill under normal pressure, collects the fraction before 80 DEG C, be denoted as fraction I, then carry out decompression steaming It evaporates, collects 80~120 DEG C of fraction, be denoted as fraction II, a certain amount of dodecane be added in fraction II, then 120~160 Continue vacuum distillation under the conditions of DEG C and collect gained fraction, is denoted as fraction III, takes out subnatant after stratification.
The ratio highest shared by ethyl levulinate in the liquefaction products of corn stover stalk, in the ethyl acetate of water phase The content of ethyl levulinate is 53% in extract liquor, while the esters such as ethyl acetate, ethyl propionate, triethyl citrate account for 32%, acid accounts for 11%, and aldehyde material accounts for 4%.
Embodiment 2
The present embodiment discloses a kind of method that purification Wheat straw fiber prepares high-efficiency diesel fuel oil additive, including following step Suddenly,
(1) wheat stalk is cleaned, drying smashes it through 70 meshes, obtains straw powder I, mixed by the volume ratio of 1:2.5 It closes nitric acid and ethyl alcohol is configured to reagent, straw powder I is added by the solid-to-liquid ratio of 1:15 into reagent, reaction kettle I is transferred to, in temperature 80 DEG C are spent, 180min is reacted under condition of normal pressure, is filtered after the reaction was completed, obtain residue I and the filtrate I dissolved with lignin, Filtrate I is reused after being handled, and is dried for standby in 100 DEG C of baking ovens after residue I is washed with distilled water, is obtained stalk Powder II；
(2) sig water is configured, the NaOH aqueous solution that mass fraction is 4% is added into reaction kettle II, by solid-to-liquid ratio 1:35 Ratio straw powder II is added, stir into suspension, be arranged 95 DEG C of temperature range, boiling 2.5h is filtered after the completion, obtained Residual II and filtrate II dissolved with hemicellulose, filtrate II are reused after being handled, by residual II distillation washing It is dried for standby in 100 DEG C of baking ovens after washing, obtains straw powder III；
(3) H that configuration concentration is 3%2O2Solution, be added into reaction kettle III, in solid-to-liquid ratio 1:30 ratio be added Straw powder III stands reaction 5h, after the completion filtrate II I, filtrate II I is filtered, is washed, dry straw powder IV；
(4) straw powder IV and methanol solution are added by the mass ratio of 1:25 to autoclave IV, its total amount is added 0.4% concentrated sulfuric acid and catalyst Patent alum 2%, after mixing evenly, sealing utilizes microwave heating, microwave power 900W is warming up to 165 DEG C in 2min, is pressurized 2MPa, insulation reaction 60min, filters to obtain filtrate IV；
(5) filtrate IV distill under normal pressure, collect the fraction before 80 DEG C, be fraction I, then carry out fraction I Vacuum distillation collects 80~120 DEG C of fraction, obtains fraction II, finally continue to depressurize under the conditions of 120~160 DEG C by fraction II Fraction is collected in distillation, is fraction III, and gained fraction III is gained diesel fuel additives.
Ratio highest shared by methyl ester levulinate in the product, by being blent with diesel oil by the volume ratio of 1:10~12, Improve 10% or more diesel oil efficiency.
It should be noted that, in this document, such as first and second or the like relational terms are used merely to one if it exists A entity or operation with another entity or operate distinguish, without necessarily requiring or implying these entities or operation it Between there are any actual relationship or orders.Moreover, the terms "include", "comprise" or its any other variant are intended to Cover non-exclusive inclusion, so that the process, method, article or equipment for including a series of elements not only includes those Element, but also including other elements that are not explicitly listed, or further include for this process, method, article or setting Standby intrinsic element.In the absence of more restrictions, the element limited by sentence "including a ...", it is not excluded that There is also other identical elements in the process, method, article or apparatus that includes the element.
The above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although with reference to the foregoing embodiments Invention is explained in detail, those skilled in the art should understand that: it still can be to aforementioned each implementation Technical solution documented by example is modified or equivalent replacement of some of the technical features；And these modification or Replacement, the spirit and scope for technical solution of various embodiments of the present invention that it does not separate the essence of the corresponding technical solution.

Claims (10)

1. a kind of efficiently purification straw base diesel fuel additives, it is characterised in that: the additive includes arriving for corn stover alcoholysis Product and the obtained mixing of product of straminol solution.
2. efficient purification straw base diesel fuel additives according to claim 1, it is characterised in that: the corn stover alcoholysis To product and the obtained mixing mass ratio of product of straminol solution be 1~2:1~5.
3. a kind of prepare the method such as the described in any item efficient purification straw base diesel fuel additives of claim 1-2, feature It is: where the preparation method of the product of the corn stover alcoholysis arrived is the following steps are included: pretreatment to corn stover Straw powder I is obtained, straw powder I progress delignification is handled into obtain filtrate I and straw powder II, straw powder II is mixed with ethanol solution It closes, stirs into suspension and add the catalyst concentrated sulfuric acid, be transferred to alcoholysis in autoclave, suction filtration obtains filtrate II, to filter Liquid II is distilled to obtain fraction III, and layering goes to inhale layer solution to be prepared corn stover alcoholysis after gained fraction III is stood The product arrived；Product preparation method that the straminol solution obtains is done the following steps are included: wheat stalk is cleaned Straw powder I is obtained after dry, crushing, mixed nitrate and ethyl alcohol are configured to reagent, straw powder I are added into reagent, carries out after reaction It filters, obtains residue I and the filtrate I dissolved with lignin, filtrate I is reused after being handled, and incites somebody to action to obtain straw powder II；Straw Stalk powder II reacts in sig water, obtains residual II and the filtrate II dissolved with hemicellulose, and filtrate II carries out weight after being handled It is multiple to use, residual II is washed, straw powder III is obtained；Straw powder III is added to H2O2Solution, after reaction, obtain filtrate II I, take out Filter, washing, dry straw powder IV；Straw powder IV is reacted with methanol solution, filters to obtain filtrate IV；Filtrate IV is steamed It evaporates, fraction, is fraction I, then fraction I is evaporated under reduced pressure, obtains fraction II, fraction II is collected in vacuum distillation finally and is evaporated Point, it is fraction III, gained fraction III is the product that straminol solution obtains.
4. preparing the method for efficiently purification straw base diesel fuel additives according to claim 1, it is characterised in that: the stalk Powder I carries out the process of delignification processing, first reagent is configured to by the volume ratio mixed nitrate and ethyl alcohol of 1:2~3, then by straw Stalk powder I is added by the solid-to-liquid ratio of 1:12~16 into reagent, is transferred to reaction kettle I, anti-under condition of normal pressure at 70~90 DEG C of temperature 150~200min is answered, is filtered after the reaction was completed, residue I and the filtrate I dissolved with lignin are obtained, after filtrate I is handled It is reused, dry 20~30h is spare in 90~105 DEG C of baking ovens after residue I is washed with distilled water, and obtains straw powder II。
5. preparing the method for efficiently purification straw base diesel fuel additives according to claim 3, it is characterised in that: the corn Stalk alcoholysis to product in the condition of alcoholysis be that reaction kettle is heated to preset 170~200 DEG C, pressure is 2.00 in kettle ~2.25MPa keeps 60~70min at this temperature.
6. preparing the method for efficiently purification straw base diesel fuel additives according to claim 3, it is characterised in that: the corn Stalk alcoholysis to product preparation method described in the process of distillation be that filtrate II is taken to distill under normal pressure, collect 80 DEG C it Preceding fraction is denoted as fraction I, is then evaporated under reduced pressure, and collects 80~120 DEG C of fraction, fraction II is denoted as, in fraction II A certain amount of dodecane is added, then continues fraction obtained by vacuum distillation collection under the conditions of 120~160 DEG C, is denoted as fraction III。
7. preparing the method for efficiently purification straw base diesel fuel additives according to claim 3, it is characterised in that: by Wheat Straw Stalk is cleaned, and drying smashes it through 60~80 meshes, is obtained straw powder I, is matched by the volume ratio mixed nitrate and ethyl alcohol of 1:2~3 It is set to reagent, straw powder I is added by the solid-to-liquid ratio of 1:12~16 into reagent, reaction kettle I is transferred to, in temperature 70~90 DEG C, 150~200min is reacted under condition of normal pressure, is filtered after the reaction was completed, obtains residue I and the filtrate I dissolved with lignin, Filtrate I is reused after being handled, and is dried for standby, is obtained in 90~105 DEG C of baking ovens after residue I is washed with distilled water Straw powder II.
8. preparing the method for efficiently purification straw base diesel fuel additives according to claim 3, it is characterised in that: the straw The NaOH aqueous solution that configuration quality score is 3~6% in the product preparation method that alcoholysis obtains is added into reaction kettle II, presses Straw powder II is added in the ratios of solid-to-liquid ratio 1:30~40, stirs into suspension, is arranged 90~110 DEG C of temperature range, and boiling 2~ 3h is filtered after the completion, obtains residual II and the filtrate II dissolved with hemicellulose, and filtrate II carries out repeating to make after being handled With being dried for standby in 90~105 DEG C of baking ovens after being washed with distilled water residual II, obtain straw powder III.
9. preparing the method for efficiently purification straw base diesel fuel additives according to claim 3, it is characterised in that: the straw The H that configuration concentration is 2~4% in the product preparation method that alcoholysis obtains2O2Solution, be added into reaction kettle III, by solid-liquid Straw powder III is added in ratio than 1:30~35, stands 5~6h of reaction, obtains filtrate II I after the completion, take out to filtrate II I Filter, washing, dry straw powder IV.
10. preparing the method for efficiently purification straw base diesel fuel additives according to claim 3, it is characterised in that: the wheat Straw powder IV and methanol solution be added by the mass ratio of 1:20~30 in the product preparation method that stalk alcoholysis obtains anti-to high pressure Kettle IV is answered, the concentrated sulfuric acid and catalyst Patent alum 1~3% of its total amount 0.3~0.6% is added, it is after mixing evenly, close Envelope, using microwave heating, 800~1000W of microwave power is warming up to 160~180 DEG C in 2min, is pressurized 2~3MPa, heat preservation 50~70min is reacted, filtrate IV is filtered to obtain.
CN201810714814.XA 2018-07-03 2018-07-03 It is a kind of efficiently to purify straw base diesel fuel additives and preparation method thereof Pending CN108949264A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810714814.XA CN108949264A (en) 2018-07-03 2018-07-03 It is a kind of efficiently to purify straw base diesel fuel additives and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810714814.XA CN108949264A (en) 2018-07-03 2018-07-03 It is a kind of efficiently to purify straw base diesel fuel additives and preparation method thereof

Publications (1)

Publication Number Publication Date
CN108949264A true CN108949264A (en) 2018-12-07

Family

ID=64485149

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810714814.XA Pending CN108949264A (en) 2018-07-03 2018-07-03 It is a kind of efficiently to purify straw base diesel fuel additives and preparation method thereof

Country Status (1)

Country Link
CN (1) CN108949264A (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101235604A (en) * 2007-01-31 2008-08-06 中国科学院化学研究所 Method for extracting cellulose from straw
CN101649569A (en) * 2009-09-01 2010-02-17 陕西科技大学 Process for preparing low-pollution wheatgrass microcrystalline cellulose
CN102659594A (en) * 2012-05-03 2012-09-12 郑州大学 Method for preparing ethyl levulinate by using straw-type biomass
CN103408422A (en) * 2013-07-25 2013-11-27 中科院广州化学有限公司 High-yield levulinic acid ester preparation method under catalysis of solid acid
CN103924468A (en) * 2014-05-16 2014-07-16 长春工业大学 Separation method of lignocellulose raw material ingredients

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101235604A (en) * 2007-01-31 2008-08-06 中国科学院化学研究所 Method for extracting cellulose from straw
CN101649569A (en) * 2009-09-01 2010-02-17 陕西科技大学 Process for preparing low-pollution wheatgrass microcrystalline cellulose
CN102659594A (en) * 2012-05-03 2012-09-12 郑州大学 Method for preparing ethyl levulinate by using straw-type biomass
CN103408422A (en) * 2013-07-25 2013-11-27 中科院广州化学有限公司 High-yield levulinic acid ester preparation method under catalysis of solid acid
CN103924468A (en) * 2014-05-16 2014-07-16 长春工业大学 Separation method of lignocellulose raw material ingredients

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
马光路等: "玉米秸秆中木质素、纤维素和半纤维素的组分分离研究", 《中国农业科技导报》 *

Similar Documents

Publication Publication Date Title
Deng et al. A feasible process for furfural production from the pre-hydrolysis liquor of corncob via biochar catalysts in a new biphasic system
Si et al. A strategy for generating high-quality cellulose and lignin simultaneously from woody biomass
Selvakumar et al. Optimization of binary acids pretreatment of corncob biomass for enhanced recovery of cellulose to produce bioethanol
CN110272509B (en) High-efficiency pretreatment separation hemicellulose of fibrous biomass and comprehensive utilization method thereof
RU2631242C2 (en) Method for preparing levulinic acid from lignocellulosic biomass
WO2011073253A1 (en) Method for producing furfural from lignocellulosic biomass material
CN107840783B (en) Method for catalytic depolymerization of biomass by molybdenum oxide catalyst
CN103757959B (en) A kind of method using ionic liquid two-step method to obtain fiber-rich cellulosic material from straw
CN109232909B (en) Method for separating high-activity lignin from agriculture and forestry biomass
Su et al. Investigation on the decomposition of chemical compositions during hydrothermal conversion of dewatered sewage sludge
CN104004582A (en) Method for preparing bio-oil reactant and bio-oil from lignocellulosic biomass
CN103360255A (en) Method for preparation of ethyl levulinate from furfural residues
CN102516209A (en) Method for coproducing furfural, ethanol and lignin from corncob
CN105950274A (en) Method for preparation of bio-oil by hydroxyl donor coordinated sub/super-critical ethanol liquefaction of straw cellulose
CN107096528A (en) A kind of bagasse carbonization load biomass-based catalyst of ruthenium and preparation method and application
CN107090303B (en) Prepared by overcritical mixed solvent liquefaction lignin is rich in aromatic compound bio oil method
CN108949264A (en) It is a kind of efficiently to purify straw base diesel fuel additives and preparation method thereof
CN103980929A (en) Method for preparing biological fuel oil by fast pyrolyzing biomass
CN108014782A (en) A kind of method of catalytic degradation lignin
CN102321489B (en) Method for catalyzing and liquefying agricultural wastes by using ion liquid
CN109628128B (en) CO (carbon monoxide)2Method for preparing furfural by hydrothermal liquefaction of agricultural and forestry waste under atmosphere
JP6274478B2 (en) Method for producing lignin degradation product
CN106904591B (en) A kind of preparation method and application of step hole tobacco rod carbon
CN102504856A (en) Method for preparing fuel oil by liquefying wood meal under normal pressure
Martinez et al. Conversion of lignocellulosic biomass in biobutanol by a NOVEL thermal process

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20181207