CN105525381B - A kind of composite polyester fiber containing graphene, preparation method and use - Google Patents

A kind of composite polyester fiber containing graphene, preparation method and use Download PDF

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CN105525381B
CN105525381B CN201510707240.XA CN201510707240A CN105525381B CN 105525381 B CN105525381 B CN 105525381B CN 201510707240 A CN201510707240 A CN 201510707240A CN 105525381 B CN105525381 B CN 105525381B
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polyester fiber
carbon nano
compound
carbon
structured
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CN201510707240.XA
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CN105525381A (en
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唐林
唐一林
张金柱
张安
吕冬生
刘顶
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济南圣泉集团股份有限公司
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Abstract

The present invention relates to a kind of composite polyester fiber containing graphene, contain graphene in the polyester fiber;The graphene is introduced by the form of carbon nano-structured compound;The carbon nano-structured compound includes graphene, and the carbon of SP3 hybrid structures.The preparation method of composite polyester fiber provided by the invention containing graphene to carbon nano-structured compound without being modified, reduce cost, technological process is simplified, realizes carbon nano-structured and polyester combination process and the preparation of normal polyester master batch and the slitless connection of spinning technique.

Description

A kind of composite polyester fiber containing graphene, preparation method and use

Technical field

The invention belongs to the technical field of composite polyester material, be related to a kind of composite polyester fiber containing graphene and its Preparation method, and in particular to a kind of composite polyester fiber containing graphene with multiple performance, and carbon need not be received The compound of rice structure is modified the method that can directly prepares composite polyester fiber, and the composite polyester fiber can answer For preparing civilian clothes, home-textile, ultraviolet protection fabric, industrial special protecting clothing.

Background technology

Polyester fiber (polyester fibre) refers to by a variety of dihydric alcohols and aromatic binary carboxylic acid or its ester through polycondensation The polyester of generation is the general designation of fiber obtained by raw material.Common polyester fiber generally comprises PET fibre Dimension, poly fiber, PTT Fiber, poly terephthalic acid-Isosorbide-5-Nitrae-cyclohexanedimethylene terephthalate The dacron fibre of fiber, the poly- ester fiber of 2,6- naphthalenes diacid second two, and a variety of modifications is (such as:CDP, ECDP, EDDP) etc..

The polyester fiber of industrial mass production is the Chinese business made of polyethylene terephthalate (PET) The name of an article is terylene, is the kind that yield is maximum in chemical fibre product, in occupation of the market share of fiber product nearly 80%;Fibre-grade gathers Ester section is supplied with the direct raw material that polyster fibre enterprise processing fiber is used to manufacture terylene short fiber and polyester filament, its chemistry Structural formula is:

PET melt is produced through over-churning and polycondensation by terephthalic acid (TPA) (PTA) and ethylene glycol (EG), PET melt passes through again Underwater cutpellet and generate PET master batch, then carry out spinning.

By taking PET as an example, the industrial synthesis technique of polyester generally comprises the main workshop section of following three:

1. raw material pulping mixes workshop section:It is main to complete raw material, including PTA (terephthalic acid (TPA)), EG (ethylene glycol), catalysis Agent, other auxiliary agents) uniform mixing;

2. the prepolymerization workshop section of polyester:The pre-polymerization merging for completing reactant forms molecular weight polymers, and this workshop section exists An esterification and class two conversion zones are often divided into complete the removing of byproduct of reaction such as water and feature in specific production The introducing of filler;

3. polycondensation workshop section:Mainly realize the mutual polymerization of molecular weight polymers, the process of chain extension thickening, in actual production The workshop section is often split as precondensation (low vacuum polymerization) and final minification poly- (high vacuum polymerization) two conversion zones.

4. spinning workshop section.

But pure polyester fiber product moisture pick-up properties is poor, easy Accumulating charge forms electrostatic under dry climate, dress and Produce electrostatic during use, comfort is difficult to compare favourably with natural cotton fiber, and (specific insulation of general synthetic fibers is 1015Ω· More than cm, and to make human body sensory comfortable, electric discharge phenomena are not produced, and the specific insulation of fiber should be 1010Below Ω cm). In addition, the antibiotic property, flame-retardant and anti-dripping, the uvioresistant that improve polyester fiber are also to improve the important side of polyester fiber application value To.

At present, on the one hand, the method that can use fiber surface post processing is real for antistatic, anti-bacterial fibre the preparation method of tradition It is existing.CN103194891A disclose a kind of production method of silver system antibacterial antistatic fiber, silver system antibacterial antistatic fiber and its The clothes of preparation, antistatic effect is realized using silver-plated method;CN101463560A discloses the antistatic fibre of abrasion performance And manufacture method and the composition for manufacturing the fiber, antistatic effect is realized using the method for coating alkyl phosphate salt.This two Although kind of method significant effect, wash durability is poor, without permanent.

Carbon nanomaterial refers to the dispersed phase yardstick at least one-dimensional carbon material less than 100nm, such as CNT, graphite Alkene etc..Graphene is a kind of two-dimensional material for the alveolate texture being made up of individual layer sp2 hydbridized carbon atoms, is had many excellent Performance.It has been found since 2004, graphene just becomes a big study hotspot of scientific circles, to the physico of graphene While property is studied, the composite related to graphene emerges in an endless stream.On nano science direction, graphene It is used to prepare the nano combined material of the nano composite material, especially graphene/metal or graphene/metal oxide of correlation Material.Due to the excellent properties of graphene, these nano composite materials are led in novel energy, bio-sensing, catalysis, optical material etc. There are wide Research Prospects in domain.

Ordinary carbon nanomaterial because its surface is without functional group, it is difficult to PET carry out it is compound, so as to hinder modified PET system The development of standby high performance material.

At present, one main path of explorative research of the graphene in terms of fiber to graphene i.e. by carrying out chemical modification Material cladding is completed again, is to use as CN103044865A discloses a kind of preparation method of amino graphene modified PET material Amination graphene carries out compound preparation PET composite material;CN103966844A discloses a kind of graphene conductive composite fibre Preparation method, be using graphene oxide carry out after fiber surface chemical modification electronation again obtain graphene be modified it is fine Dimension;Such method is required to be modified graphene processing, and the intrinsic excellent specific property of one side graphene is deteriorated significantly, separately One side industrial production cost is too high, and environmental protection production pressure is big, while is difficult to avoid that product function unification, performance and cost Than it is not high the problem of.

CN103938293A discloses a kind of far-infrared polyester fiber and preparation method thereof, the original of the far-infrared polyester fiber Material includes according to parts by weight configuration:15~35 parts of 65~85 parts of polyester slice and far-infrared matrix, the far-infrared matrix Raw material includes according to parts by weight configuration:75~90 parts of polyester slice, 10~20 parts of nano-far-infrared powder, silane coupler 0.5~5 part, 0.5~5 part of Tissuemat E, three 0.05~1 part of [2.4- di-tert-butyl-phenyls] phosphite esters and four [β-(3,5- bis- Tert-butyl-hydroxy phenyl) propionic acid] 0.05~1 part of pentaerythritol ester.

CN1308148A discloses a kind of far infrared radiating hollow 3-D crimped polyester fiber and preparation method thereof, by 0.3 ~0.5 μm of composite inorganic far infrared super-fine material, high-speed stirring is together added to titante coupling agent and surfactant Progress dry surface processing, the super-fine material powder after surface treatment in machine is mixed to mix in high-speed mixer with polyester support, Obtained mixed powder is sent to blending extrusion in double screw extruder, its operating temperature is more conventional make Masterbatch temperature it is low 10~ 30 DEG C, far-infrared matrix obtained above and polyester slice are delivered into blender through feeder charging and mixed, is then sent to The extruder type spinning machine for making hollow 3-D crimped fiber carries out spinning, and the finished product finally obtained is that Far-infrared spoke of the present invention is hit Empty 3-D crimped polyester fiber.A variety of far infrared inorganic material, its fundamental component are silica, alundum (Al2O3), two The mixture of titanium oxide, zirconium dioxide, is crushed with superfine jet mill, is crushed to its particle diameter at 0.3~0.5 μm, will be crushed Far infrared inorganic material powder afterwards, which is placed in high temperature furnace, to be sintered, and sintering temperature is 800~1100 DEG C, powder again after sintering cooling It is broken, particle diameter is still controlled and at 0.3~0.5 μm, obtain 0.3~0.5 μm of composite inorganic far infrared super-fine material.

The content of the invention

The goal of the invention of the present invention is to provide that a kind of technique is simple, and cost is cheap, and can prepare with antibacterial, remote The preparation method of the composite polyester fiber containing graphene of infrared effect.

In order to reach goal of the invention, present invention employs following technical scheme:

In a first aspect, the invention provides a kind of composite polyester fiber containing graphene, contain in the polyester fiber Graphene;

The graphene is introduced by the form of carbon nano-structured compound;The carbon nano-structured compound includes Graphene, and the carbon of SP3 hybrid structures.

The present invention is used as compound material from specific carbon nano-structured compound, with compound to polyester material progress, Without being modified in advance to carbon nano-structured compound, it is only necessary to simply add carbon nano-structured compound existing In the polymerization technique of polyester fiber.

The carbon nano-structured compound far infrared detection normal emittance be more than 0.85, such as 0.87,0.89, 0.91st, 0.92,0.93 etc., preferably greater than 0.88.

Also include graphene nanometer sheet in the carbon nano-structured compound.

In the carbon nano-structured compound, content >=80wt% of the carbon, such as 82wt%, 86wt%, 89wt%, 91wt%, 94wt%, 97wt%, 99wt% etc., preferably 85~97wt%, further preferred 90~95wt%.

Preferably, carbon nano-structured compound carbon G peaks and D peaks peak height ratios under Raman spectrum be 1~ 20, such as 2,5,7,8,10,12,13,16,18 etc., preferably 2~20, further preferred 3~20.

Carbon G peaks embody sp2 hydridization degree under Raman spectrum;D peaks embody lattice defect, such as sp3 carbon knot Structure.

Carbon nano-structured compound of the present invention is a kind of compound containing impurity element based on carbon, Wherein carbon mainly exists in the form of sp2 hydridization.

Preferably, in the composite polyester fiber, the content of carbon nano-structured compound is 0.1~10wt%, such as 0.2wt%, 1wt%, 3wt%, 4wt%, 6wt%, 8wt%, 9wt% etc., preferably 0.5~7wt%, further preferred 1~ 5wt%, particularly preferred 2~4wt%.

Preferably, the carbon nano-structured compound of the sandwich layer of the carbon nano-structured compound composite polyester fiber is dense Degree is lower than the carbon nano-structured complex concentration of cortex.

Preferably, the carbon nano-structured compound contains carbon, 0.5~4wt% the first non-carbon nonoxygen element Second non-carbon nonoxygen element of material and 0~4wt%, the first non-carbon nonoxygen element material are the first non-carbon nonoxygen element Any a kind or at least two kinds of of combination in simple substance, compound;The first non-carbon nonoxygen element is P, Si, Ca, Al and Na;Institute The second non-carbon nonoxygen element is stated in the form of any a kind or at least two kinds of in simple substance, compound of combination to exist;Described second Any a kind or at least two kinds of of combination of the non-carbon nonoxygen element in Fe, Ni, Mn, K, Mg, Cr, S or Co.

Preferably, carbon nano-structured compound has hexatomic ring cellular lamella knot of the thickness in below 100nm carbon Structure, preferably with thickness below 20nm carbon the cellular lamellar structure of hexatomic ring, further preferably have the number of plies be 1~10 Any a kind or at least two kinds of of combination in the cellular lamellar structure of hexatomic ring of layer carbon, preferred single layer, bilayer or 3~10 layers of knot Any a kind or at least two kinds of of combination in structure.

The number of plies is more than 10 layers, the thickness cellular lamellar structure of the hexatomic ring of carbon, referred to as graphene nanometer sheet within 100nm Layer, using biomass be the number of plies for preparing of carbon source more than 10 layers, thickness cellular lamellar structure of the hexatomic ring of carbon within 100nm, Referred to as biomass graphene nano lamella;The number of plies is the cellular lamellar structure of hexatomic ring of 1~10 layer of carbon, referred to as graphene, with Biomass is the cellular lamellar structure of hexatomic ring that the number of plies prepared by carbon source is 1~10 layer of carbon, referred to as biomass graphene.

Preferably, the microcosmic upper presentation warpage of the cellular lamellar structure of hexatomic ring of carbon, curling, folding structure in the compound Any a kind or at least two kinds of of the combination as in.

Microscopic appearance on the lamellar structure in compound can typically be obtained by electron microscope observation, can be with It is transmission electron microscope or ESEM.

Preferably, in the carbon nano-structured compound, the first non-carbon nonoxygen element is with simple substance, oxide or carbide In any a kind or at least two kinds of of combination form adsorb on carbon nano-structured surface or inside.

Preferably, in the carbon nano-structured compound, the first non-carbon nonoxygen element is introduced by carbon source;The carbon source It is preferred that biomass carbon source, any a kind or at least two kinds of of combination of the biomass resource in plant and/or agriculture and forestry organic waste material;It is excellent Select any a kind or at least two kinds of of combination in needlebush, leaf wood, Lin Yemu, agriculture and forestry organic waste material;The agriculture and forestry organic waste material is excellent In cornstalk, corncob, kaoliang stalk, megasse, bagasse, furfural dregs, xylose residue, wood chip, cotton stalk, shell and reed Any a kind or at least two kinds of of combination, preferred corncob.

The present invention is not specifically limited to the species of polyester, and typical but non-limiting polyester includes poly terephthalic acid second It is diester, polybutylene terephthalate (PBT), polytrimethylene terephthalate, polycyclohexane terephthalate, poly- 2,6- naphthalenes diacid second diester and the PET of a variety of modifications are (such as:CDP, ECDP, EDDP) etc., Ren Heyi The polyester that kind those skilled in the art can be known is used equally for the present invention.Preferably industrial mass production PET polyester of the invention.

Second aspect, present invention also offers a kind of system of the composite polyester fiber containing graphene as described in relation to the first aspect Preparation Method, methods described are:

Carbon nano-structured compound is introduced during polyester in-situ polymerization, reaction finishes to obtain melt, and melt discharges, Pelletizing obtains complex polyester master batch, complex polyester master batch melt spinning, obtains the composite polyester fiber containing graphene;It is preferred that , when introducing carbon nano-structured compound, without to its modification.

The present invention uses in-situ polymerization, and carbon nano-structured compound is added before the completion of polyester fiber polymerisation Enter, improve stability of the carbon nano-structured compound in polyester fiber, ensure that the complex polyester containing graphene is fine The functional result of dimension it is permanent, such as washability.

Preferably, the melt-spinning technology is preoriented yarn technique;

Preferably, the wire vent temperature of the preoriented yarn be 30~70 DEG C, such as 33 DEG C, 36 DEG C, 38 DEG C, 45 DEG C, 50 DEG C, 53 DEG C, 58 DEG C, 63 DEG C, 66 DEG C, 69 DEG C etc., wire vent humidity be 10~90%, such as 15%, 18%, 22%, 28%, 35%, 42%th, 48%, 54%, 59%, 65%, 80%, 88% etc.;It is preferred that wire vent temperature be 55~65 DEG C, wire vent humidity be 40~ 50%;Further preferred wire vent temperature is 62 DEG C, and wire vent humidity is 42%.

Preferably, the wire vent uses air-cooled or water cooling.

Preferably, the temperature of cooling water is 20~75 DEG C during melt discharging, for example, 25 DEG C, 28 DEG C, 34 DEG C, 38 DEG C, 45 DEG C, 57 DEG C, 64 DEG C, preferably 70 DEG C, 73 DEG C etc., 40 DEG C.

Preferably, the draft speed of melt discharging is 0.01~1m/s, for example, 0.03m/s, 0.1m/s, 0.24m/s, 0.35m/s, 0.47m/s, 0.54m/s, 0.67m/s, 0.75m/s, 0.82m/s, 0.98m/s etc..

Preferably, the addition of the carbon nano-structured compound is 0.1~10wt% of polyester fiber, such as 0.5wt%, 2wt%, 3wt%, 5wt%, 10wt% etc., preferably 0.5~7wt%, further preferred 1~5wt%, particularly preferably 2~4wt%.The addition of carbon nano-structured compound is too low, additional properties unobvious, too high, causes the big of product cost Amplitude improves and the deterioration of product mechanical property.

Preferably, the carbon nano-structured compound is added in the form of carbon nano-structured compound dry powder, or Added in the form of carbon nano-structured compound dispersion liquid.

Preferably, the dispersant of the carbon nano-structured compound dispersion liquid be selected from deionized water, distilled water, ethanol, Any a kind in ethylene glycol, terephthalic acid (TPA), sodium acetate solution, DBSA, castor oil polyoxyethylene ether or at least 2 kinds of combination.

Preferably, in polyester fiber process, the addition opportunity of carbon nano-structured compound is selected from raw material pulping Any a kind or at least two kinds of of combination in stage, esterification prepolymerisation stage, precondensation stage, whole polycondensation phase, is preferably original Expect the mashing stage.

On the addition opportunity of the suitable carbon nano-structured compound of selection, polymeric articles performance can be affected.In original Expect that the mashing stage adds, carbon nano-structured compound can participate in esterification by its a small amount of epoxide group, in complex Dispersiveness is more preferable in system.

" at least two kinds of combinations " on the addition opportunity of carbon nano-structured compound of the present invention refer to can be in polyester The different opportunitys of fiber process add carbon nano-structured compound, such as can be simultaneously in raw material pulping stage and ester Change prepolymerisation stage and add carbon nano-structured compound, or add carbon nanometer in precondensation stage and whole polycondensation phase simultaneously The compound of structure, or it is simultaneously carbon nano-structured in raw material pulping stage, esterification prepolymerisation stage and the addition of whole polycondensation phase Compound etc..

Preferably, the addition time of the carbon nano-structured compound per kilogram is 30s~30min, such as 35s, 50s, 2min, 5min, 8min, 12min, 17min, 23min, 28min etc..

As optimal technical scheme, the preparation method of the composite polyester fiber of the present invention containing graphene is including as follows Step:

(1) reactor is put into after the mashing of polyacid, polyalcohol and carbon nano-structured compound is mixed, is made in catalyst Under, polymerisation is completed in esterification and polycondensation, obtains melt;

(2) melt discharges under conditions of 20~75 DEG C of cooling waters, 0.01~1m/s draft speeds, is directly granulated and obtains mother Grain;

(3) by master batch at 30~70 DEG C of wire vent temperature, 10~90% wire vent damp conditions, using air-cooled or water cooling, melt Melt spinning, obtain the composite polyester fiber containing graphene.

Preferably, carbon nano-structured compound of the present invention obtains by the following method:

(i) mixing biomass carbon source and catalyst, after stirring carries out catalytic treatment, it is dried to obtain presoma;

(ii) in protective atmosphere, by presoma at 280~350 DEG C, such as 282 DEG C, 288 DEG C, 295 DEG C, 300 DEG C, 332 DEG C, 340 DEG C etc., be incubated 1.5~2.5h, such as 1.6h, 1.8h, 2h, 2.2h, 2.4h etc., temperature programming afterwards to 950~1200 DEG C, such as 960 DEG C, 970 DEG C, 980 DEG C, 990 DEG C, 1010 DEG C, 1020 DEG C, 1030 DEG C, 1040 DEG C etc., 3~4h is incubated, such as 3.1h, 3.3h, 3.5h, 3.8h, 3.9h etc., obtain crude product;The heating rate of described program heating is 15~20 DEG C/min, such as 16 DEG C/min, 18 DEG C/min, 19 DEG C/min etc.;

(iii) after crude product is washed, carbon nano-structured compound is obtained;

Preferably, the mass ratio of the biomass carbon source and catalyst is 1:0.1~10, such as 1:2、1:4、1:6、1:8 Deng preferably 1:0.5~5, further preferred 1:1~3;

Preferably, in compound of the catalyst selected from manganese, iron containing compoundses, cobalt compound and nickel compound containing Any a kind or at least two kinds of of combination;The iron containing compoundses are selected from the halogen compounds of iron, the cyanide and iron content hydrochlorate of iron In any a kind or at least two kinds of of combination;Halogen compounds of the cobalt compound selected from cobalt and containing any in cobaltatess 1 kind or at least two kinds of of combination;Chlorate of the nickel compound containing selected from nickel and containing any a kind in nickelate or at least two kinds of Combination.

It is further preferred that the catalyst is selected from iron chloride, frerrous chloride, ferric nitrate, ferrous nitrate, ferric sulfate, sulphur Sour ferrous iron, the potassium ferricyanide, potassium ferrocyanide, three oxalic acid conjunction potassium ferrite, cobalt chloride, cobalt nitrate, cobaltous sulfate, cobalt acetate, nickel chloride, Any a kind or at least two kinds of of combination in nickel nitrate, nickel sulfate and nickel acetate.

The typical but non-limiting example of combination of catalyst of the present invention has the combination of frerrous chloride and ferric sulfate, iron Potassium cyanide and three oxalic acid close the combination of potassium ferrite, the combination of cobalt chloride, cobalt nitrate and iron chloride, cobaltous sulfate, cobalt acetate and nitric acid The combination of nickel, the combination of iron chloride, cobalt chloride and nickel acetate etc..

Preferably, step (i) it is described stirring carry out catalytic treatment temperature be 150~200 DEG C, such as 160 DEG C, 170 DEG C, 180 DEG C 190 DEG C etc., the time >=4h, such as 4.2h, 7h, 9h, 12h, 16h, 19h, 23h etc., preferably 4~14h;The presoma In moisture be preferably below 10wt%, such as 1wt%, 2wt%, 3wt%, 4wt%, 5wt%, 6wt%, 7wt%, 8wt%, 1wt% etc.;The heating rate that step (ii) described presoma is warming up to 280~350 DEG C is preferably 3~5 DEG C/min, example Such as 3.5 DEG C/min, 3.8 DEG C/min, 4.2 DEG C/min, 4.5 DEG C/min, 4.8 DEG C/min;The protective atmosphere is nitrogen, helium Any a kind or at least two kinds of of combination in gas, argon gas, preferably nitrogen;Step (iii) the crude product washing is carried out successively Pickling and washing;The preferred concentration of pickling is 3~6wt% hydrochloric acid, and further preferred concentration is 5wt% hydrochloric acid; The washing preferably uses deionized water and/or distilled water;The temperature of the washing be 55~65 DEG C, such as 56 DEG C, 57 DEG C, 58 DEG C, 60 DEG C, 63 DEG C etc., preferably 60 DEG C.

Preferably, the biomass carbon source is cellulose and/or lignin, preferred cellulose, further preferred porous fibre Dimension element.

Porous cellulose of the present invention can be obtained by prior art, typical but non-limiting acquisition porous fibre The prior art of element has:Such as method disclosed in patent publication No. CN104016341A prepares porous cellulose, use Method prepares cellulose disclosed in CN103898782A.

Preferably, the porous cellulose obtains by the following method:

Biomass resource progress sour water solution is obtained into lignocellulosic, post-processes to obtain porous fibre afterwards by porous Element;Alternatively, porous cellulose uses after bleaching;The biomass resource preferably is selected from plant and/or agriculture and forestry organic waste material Any a kind or at least two kinds of of combination;It is preferred that any a kind or at least two kinds of of combination in agriculture and forestry organic waste material;The agricultural are discarded Thing preferably is selected from cornstalk, corncob, kaoliang stalk, megasse, bagasse, furfural dregs, xylose residue, wood chip, cotton stalk and reed Any a kind or at least two kinds of of combination, preferably corncob.

The typical but non-limiting example combinations of biomass resource of the present invention include the combination of cornstalk and corncob, The combination of bagasse, kaoliang stalk and wood chip, megasse, the combination of bagasse and corncob, kaoliang stalk, megasse and xylose residue Combination etc..

Third aspect present invention is a kind of use of the composite polyester fiber containing graphene as described in one of second aspect On the way, the composite polyester fiber containing graphene is used to prepare civilian clothes, home-textile, ultraviolet protection fabric, work Industry special protecting clothing etc., including but not limited to the said goods, as long as the complex polyester being prepared using the principle of the invention The product that fiber obtains any type of textile, fabric or other forms by reprocessing means belongs to what the present invention protected Category.

Compared with prior art, the present invention has the advantages that:

(1) preparation method of the composite polyester fiber provided by the invention containing graphene is without answering carbon nano-structured Compound is modified, and is retained the intrinsic excellent properties of carbon nano-structured compound, is reduced cost, simplify technological process;And And directly can be prepared using existing polyester synthesis and spinning equipment, it is compound to realize carbon nano-structured compound Polyester combination process is prepared with normal polyester master batch and the slitless connection of spinning technique, is easy to industrialization promotion;

(2) composite polyester fiber containing graphene that the present invention is prepared need not be post-processed and can be expected Multiple excellent properties, such as far infrared normal emittance can reach more than 0.85, and have good fungistatic effect.

Embodiment

Technical scheme is further illustrated below by embodiment.

Those skilled in the art it will be clearly understood that the embodiment be only to aid in understand the present invention, be not construed as to this hair Bright concrete restriction.

The preparation of carbon nano-structured compound

(1) it is specially with reference to CN104016341A index porous celluloses:

At 90 DEG C, with the sulfuric acid adjusting corn core aqueous solution to pH=3, immersion 10min is hydrolyzed, and obtains wood fibre Element, the quality of the sulfuric acid are the 3% of the corncob quality;Then, at 70 DEG C, obtained lignocellulosic is immersed in 1h in acid accumulator sulfite, obtains porous cellulose;Wherein, acid is sulfuric acid, and sulphite is magnesium sulfite, the matter of the sulfuric acid Measure as the 4% of the lignocellulosic quality, liquid-solid ratio 2:1;It is made rear standby;

(2) carbon nano-structured compound is prepared, is specially:

In mass ratio 1:0.1~10 mixing porous cellulose and catalyst, stir at 150~200 DEG C and carry out at catalysis More than 4h is managed, dries to below presoma moisture 10wt%, obtains presoma;Then, in protective atmosphere, with 3~5 DEG C/presoma is warming up to 280~350 DEG C by min speed, 1.5~2.5h is incubated, temperature programming afterwards is protected to 950~1200 DEG C 3~4h of temperature obtains crude product;The heating rate of described program heating is 15~20 DEG C/min;At 55~65 DEG C, crude product is passed through After concentration is 3~6wt% chlorohydric acid pickling, washing obtains carbon nano-structured compound.

The preparation condition of compound carbon nano-structured 1# is:

In step (2), catalyst is frerrous chloride;The mixing quality of porous cellulose and catalyst ratio is 1:0.1;Catalysis Treatment temperature is 150 DEG C, time 4h;Moisture in presoma is 10wt%;

The process for obtaining crude product is:280 DEG C are warming up to 3 DEG C/min speed, 2h is incubated, afterwards with 15 DEG C/min speed Rate is warming up to 950 DEG C, is incubated 3h;

Pickling temperature is 55 DEG C, and the concentration of hydrochloric acid that pickling uses is 4wt%;

P, Si, Ca, Al, Na, Fe, Mg element are mainly contained in compound carbon nano-structured 1#;And Raman spectrum shows G Peak, D peaks peak height ratios are highly than being 7;2D peaks be present;

The difference of the preparation process of compound carbon nano-structured 2# and the preparation process of compound carbon nano-structured 1# It is only that:The ratio of porous cellulose and frerrous chloride is changed into 1 in step (2):10;Compound carbon nano-structured obtained 2# In mainly contain P, Si, Ca, Al, Na, Fe, Mg element;And Raman spectrum shows G peaks, D peaks peak height ratios highly than being 20.

The difference of the preparation process of compound carbon nano-structured 3# and the preparation process of compound carbon nano-structured 1# It is only that:The ratio of porous cellulose and frerrous chloride is changed into 1 in step (2):0.5;Carbon nano-structured compound of obtained 2# P, Si, Ca, Al, Na, Fe, Mg element are mainly contained in thing;And Raman spectrum shows G peaks, D peaks peak height ratios highly than being 1.5.

Embodiment 1

A kind of composite polyester fiber, it is prepared via a method which to obtain:

(1) compound carbon nano-structured 100g and 8.52kg PTA, 3.5L ethylene glycol are fed intake mixing, ball-milling treatment Mashing kettle mashing 30min is introduced directly into after 20min, is reacted, polymerize instead according to using three kettle PET polymerization techniques Should, polymerisation finishes to obtain melt;

(2) melt obtains carbon nano-structured in 40 DEG C of cooling waters, directly 0.5m/s draft speed condition bottom discharges, granulation The compound PET master batch of compound;

(3) the carbon nano-structured compound PET master batch of compound after drum dried 24h, is directly used in molten at 110 DEG C Melt spinning, spinning wire vent is cooled down using water smoke, 40 DEG C of chilling temperature, 35 DEG C of drying temperature, and melt spinning obtains complex polyester fibre Dimension.

Respectively with compound carbon nano-structured 1#, 2# carbon nano-structured compound, 3# carbon nano-structured compound Polyester fiber is prepared, is designated as product 1a (the compound polyester fiber of compound carbon nano-structured 1#) respectively, product 1b (receive by 1# carbon The compound polyester fiber of compound of rice structure) and product 1c (the compound polyester fiber of compound carbon nano-structured 3#);

Product 1a far infrareds normal emittance can reach 0.87;It is 70% to staphylococcus aureus antibacterial bacteriostatic rate;Production Product 1b far infrareds normal emittance can reach 0.89;It is 82% to staphylococcus aureus antibacterial bacteriostatic rate;Product 1c far infrareds Normal emittance can reach 0.85;It is 65% to staphylococcus aureus antibacterial bacteriostatic rate;

Wherein, infrared detection data foundation:Through national textile fabrics Quality Supervision and Inspection Center, according to FZ/T64010- 2000 methods of inspection are tested;

Antibacterial detection data foundation:Through national textile fabrics Quality Supervision and Inspection Center, according to GB/T20944.3-2008 The method of inspection.

Embodiment 2:

A kind of composite polyester fiber, it is prepared via a method which to obtain:

(1) compound carbon nano-structured 200g and 8.52kg PTA, 3.5L ethylene glycol are fed intake mixing, ball-milling treatment Mashing kettle mashing 30min is introduced directly into after 20min, is reacted, polymerize instead according to using three kettle PET polymerization techniques Should, polymerisation finishes to obtain melt;

(2) melt obtains carbon nano-structured in 40 DEG C of cooling waters, directly 0.5m/s draft speed condition bottom discharges, granulation The compound PET master batch of compound;

(3) the carbon nano-structured compound PET master batch of compound after drum dried 24h, is directly used in molten at 110 DEG C Melt spinning, spinning wire vent is cooled down using water smoke, and 40 DEG C of chilling temperature, 35 DEG C of drying temperature, melt spinning obtains carbon nano-structured Compound composite polyester fiber.

Respectively with compound carbon nano-structured 1#, 2# carbon nano-structured compound, 3# carbon nano-structured compound Polyester fiber is prepared, is designated as product 2a (the compound polyester fiber of compound carbon nano-structured 1#) respectively, product 2b (receive by 1# carbon The compound polyester fiber of compound of rice structure) and product 2c (the compound polyester fiber of compound carbon nano-structured 3#);

Its far infrared normal emittance of product 2a can reach 0.90;It is 95% to staphylococcus aureus antibacterial bacteriostatic rate; Its far infrared normal emittance of product 2b can reach 0.92;It is 97% to staphylococcus aureus antibacterial bacteriostatic rate;Product 2c its Far infrared normal emittance can reach 0.88;It is 90% to staphylococcus aureus antibacterial bacteriostatic rate;

Method of testing is same as Example 1.

Embodiment 3:

A kind of composite polyester fiber, it is prepared via a method which to obtain:

(1) PTA 8.52kg, EG 3.5L and catalyst glycol antimony 3.8g, 30min is beaten, is gathered according to using three kettle PET Close technique to be reacted, carry out polymerisation, polymerisation finishes to obtain melt;

(2) melt is dissolved in trifluoroacetic acid, adds the carbon nano-structured compound grinding 10min of 200g, disperse equal It is even;

In 40 DEG C of cooling waters, 0.5m/s draft speed condition bottom discharges, directly it is granulated and obtains carbon nano-structured answer The compound PET master batch of compound;

(3) the carbon nano-structured compound PET master batch of compound after drum dried 24h, is directly used in molten at 110 DEG C Melt spinning, spinning wire vent is cooled down using water smoke, and 40 DEG C of chilling temperature, 35 DEG C of drying temperature, melt spinning obtains carbon nano-structured Compound composite polyester fiber.

Respectively with compound carbon nano-structured 1#, 2# carbon nano-structured compound, 3# carbon nano-structured compound Polyester fiber is prepared, is designated as product 3a (the compound polyester fiber of compound carbon nano-structured 1#) respectively, product 3b (receive by 1# carbon The compound polyester fiber of compound of rice structure) and product 3c (the compound polyester fiber of compound carbon nano-structured 3#);

Its far infrared normal emittance of product 3a can reach 0.89;It is 90% to staphylococcus aureus antibacterial bacteriostatic rate; Its far infrared normal emittance of product 3b can reach 0.90;It is 95% to staphylococcus aureus antibacterial bacteriostatic rate;Product 3c its Far infrared normal emittance can reach 0.87;It is 88% to staphylococcus aureus antibacterial bacteriostatic rate;

Method of testing is same as Example 1.

Embodiment 4:

A kind of composite polyester fiber, it is prepared via a method which to obtain:

(1) 600mL ethylene glycol is incorporated into the mashing kettle containing 8.52kg PTA and 3L ethylene glycol, adds antimony glycol 3.8g Continue to be beaten 30min, reacted according to using three kettle PET polymerization techniques, carry out polymerisation, polymerisation, which finishes, to be melted Body;Excessive EG should be excluded in the class and polycondensation of polymerisation;

(2) the carbon nano-structured compound grinding 10min of 300g will after melt heating melting, be added;

Melt obtains carbon nano-structured answer in 40 DEG C of cooling waters, directly 0.5m/s draft speed condition bottom discharges, granulation The compound PET master batch of compound;

(3) the carbon nano-structured compound PET master batch of compound after drum dried 24h, is directly used in molten at 110 DEG C Melt spinning, spinning wire vent is cooled down using water smoke, and 40 DEG C of chilling temperature, 35 DEG C of drying temperature, melt spinning obtains carbon nano-structured Compound composite polyester fiber.

Respectively with compound carbon nano-structured 1#, 2# carbon nano-structured compound, 3# carbon nano-structured compound Polyester fiber is prepared, is designated as product 4a (the compound polyester fiber of compound carbon nano-structured 1#) respectively, product 4b (receive by 1# carbon The compound polyester fiber of compound of rice structure) and product 4c (the compound polyester fiber of compound carbon nano-structured 3#);

Product 4a far infrareds normal emittance can reach 0.91;It is 99% to staphylococcus aureus antibacterial bacteriostatic rate;Production Product 4b far infrareds normal emittance can reach 0.93;It is 99% to staphylococcus aureus antibacterial bacteriostatic rate;Product 4c far infrareds Normal emittance can reach 0.89;It is 93% to staphylococcus aureus antibacterial bacteriostatic rate;

Method of testing is same as Example 1.

Embodiment 5:

A kind of composite polyester fiber, it is prepared via a method which to obtain:

(1) in the mashing kettle for weighing 8.52kg PTA and 3.5L ethylene glycol, antimony glycol 3.8g is added to be beaten 30min, according to An esterification is carried out using three kettle PET polymerization process conditions, after one is esterified 40min, batch turning to class kettle, by ball milling 20min carbon nano-structured compound/ethylene glycol slurry (compound carbon nano-structured 100g/200mL ethylene glycol) introduces To class kettle, complete subsequent polymerisation reaction and obtain melt;Excessive EG should be excluded in the class and polycondensation of polymerisation;

(2) melt obtains carbon nano-structured in 40 DEG C of cooling waters, directly 0.5m/s draft speed condition bottom discharges, granulation The compound PET master batch of compound;

(3) the carbon nano-structured compound PET master batch of compound after drum dried 24h, is directly used in molten at 110 DEG C Melt spinning, spinning wire vent is cooled down using water smoke, and 60 DEG C of chilling temperature, 40 DEG C of drying temperature, melt spinning obtains carbon nano-structured Compound composite polyester fiber.

Respectively with compound carbon nano-structured 1#, 2# carbon nano-structured compound, 3# carbon nano-structured compound Polyester fiber is prepared, is designated as product 5a (the compound polyester fiber of compound carbon nano-structured 1#) respectively, product 5b (receive by 1# carbon The compound polyester fiber of compound of rice structure) and product 5c (the compound polyester fiber of compound carbon nano-structured 3#);

Product 5a far infrareds normal emittance can reach 0.87;It is 68% to staphylococcus aureus antibacterial bacteriostatic rate;Production Product 5b far infrareds normal emittance can reach 0.88;It is 75% to staphylococcus aureus antibacterial bacteriostatic rate;Product 5c far infrareds Normal emittance can reach 0.85;It is 60% to staphylococcus aureus antibacterial bacteriostatic rate;

Method of testing is same as Example 1.

Embodiment 6:

It is that it is 500g to add carbon nano-structured compound with the distinctive points of embodiment 1.

Polyester fiber is prepared with the compound that 1# is carbon nano-structured, being designated as product 6a, (compound carbon nano-structured 1# is answered The polyester fiber of conjunction);

Product 6a far infrareds normal emittance can reach 0.92;It is 99% to staphylococcus aureus antibacterial bacteriostatic rate;

Method of testing is same as Example 1.

Embodiment 7

It is that it is 1000g to add carbon nano-structured compound with the distinctive points of embodiment 1.

Polyester fiber is prepared with the compound that 1# is carbon nano-structured, being designated as product 7a, (compound carbon nano-structured 1# is answered The polyester fiber of conjunction);

Product 7a far infrareds normal emittance can reach 0.93;It is 99% to staphylococcus aureus antibacterial bacteriostatic rate;

Method of testing is same as Example 1.

Embodiment 8

It is that it is 1200g to add carbon nano-structured compound with the distinctive points of embodiment 1.

Polyester fiber is prepared with the compound that 1# is carbon nano-structured, being designated as product 8a, (compound carbon nano-structured 1# is answered The polyester fiber of conjunction);

Product 8a far infrareds normal emittance can reach 0.93;It is 99% to staphylococcus aureus antibacterial bacteriostatic rate;

Method of testing is same as Example 1.

Comparative example 1

Carbon nano-structured compound is added without in polyester polymerization process with differing only in for embodiment 1.

Polyester fiber prepared by comparative example 1, far infrared normal emittance can reach 0.76;To staphylococcus aureus antibacterial Bacteriostasis rate is 0%;

Method of testing is same as Example 1.

Comparative example 2

It is with the distinctive points of embodiment 1:Replaced using quality such as amorphous carbon nanostructureds carbon nano-structured compound Thing.

Polyester material prepared by comparative example 2, far infrared normal emittance can reach 0.80;To staphylococcus aureus antibacterial Bacteriostasis rate is 30%;

Method of testing is same as Example 1.

Comparative example 3

It is that it is 1400g to add carbon nano-structured compound with the distinctive points of embodiment 1.

The far infrared normal emittance for the polyester fiber that comparative example 3 is prepared with compound carbon nano-structured 1# can reach 0.83;It is 80% to staphylococcus aureus antibacterial bacteriostatic rate;

Method of testing is same as Example 1.

Comparative example 4

A kind of preparation method of composite polyester fiber, actual conditions compared with Example 1, are differed only in without using implementation The carbon nano-structured compound prepared in example, but prepared in the graphene alternate embodiment commercially available from using carbon nano-structured multiple Compound, and with 1g phosphorus pentoxides, 1g SiO 2 powders, 1g parts calcium chloride, 1g alundum (Al2O3)s, 1g sodium carbonate, 1g chlorinations Added after magnesium and the mixing of 1g frerrous chlorides in PPG, introduce P, Si, Ca, Al, Na, Fe, Mg element, Raman spectrum is shown G peaks, D peaks peak height ratios are highly than being 6.8.

Polyester fiber prepared by comparative example 4, far infrared normal emittance can reach 0.87;To staphylococcus aureus antibacterial Bacteriostasis rate is 88%.

Method of testing is same as Example 1.

Applicant states that the present invention illustrates the process of the present invention, but not office of the invention by above-described embodiment It is limited to above-mentioned processing step, that is, does not mean that the present invention has to rely on above-mentioned processing step and could implemented.Art Technical staff it will be clearly understood that any improvement in the present invention, equivalence replacement and auxiliary element to raw material selected by the present invention Addition, selection of concrete mode etc., within the scope of all falling within protection scope of the present invention and disclosing.

Claims (68)

1. a kind of composite polyester fiber containing graphene, it is characterised in that contain graphene in the polyester fiber;
The graphene is introduced by the form of carbon nano-structured compound;The carbon nano-structured compound includes graphite Alkene, and the carbon of SP3 hybrid structures;
The carbon nano-structured compound contain carbon, 0.5~4wt% the first non-carbon nonoxygen element material and 0~ 4wt% the second non-carbon nonoxygen element, the first non-carbon nonoxygen element material are simple substance, the chemical combination of the first non-carbon nonoxygen element Any a kind or at least two kinds of of combination in thing;The first non-carbon nonoxygen element is P, Si, Ca, Al and Na;Described second is non- Carbon nonoxygen element exists in the form of any a kind or at least two kinds of in simple substance, compound of combination;Second non-carbon is non-oxygen Any a kind or at least two kinds of of combination of the element in Fe, Ni, Mn, K, Mg, Cr, S or Co.
2. composite polyester fiber as claimed in claim 1, it is characterised in that the far infrared inspection of the carbon nano-structured compound Survey normal emittance and be more than 0.85.
3. composite polyester fiber as claimed in claim 1, it is characterised in that the far infrared inspection of the carbon nano-structured compound Survey normal emittance and be more than 0.88.
4. composite polyester fiber as claimed in claim 1, it is characterised in that described in the carbon nano-structured compound Content >=80wt% of carbon.
5. composite polyester fiber as claimed in claim 1, it is characterised in that described in the carbon nano-structured compound The content of carbon is 85~97wt%.
6. composite polyester fiber as claimed in claim 1, it is characterised in that described in the carbon nano-structured compound The content of carbon is 90~95wt%.
7. composite polyester fiber as claimed in claim 1, it is characterised in that also include stone in the carbon nano-structured compound Black alkene nanometer sheet.
8. composite polyester fiber as claimed in claim 1, it is characterised in that the carbon nano-structured compound is in Raman light The lower carbon G peaks of spectrum and D peaks peak height ratios are 1~20.
9. composite polyester fiber as claimed in claim 1, it is characterised in that the carbon nano-structured compound is in Raman light The lower carbon G peaks of spectrum and D peaks peak height ratios are 2~20.
10. composite polyester fiber as claimed in claim 1, it is characterised in that the carbon nano-structured compound is in Raman Carbon G peaks and D peaks peak height ratios are 3~20 under spectrum.
11. composite polyester fiber as claimed in claim 1, it is characterised in that carbon nano-structured in the composite polyester fiber The content of compound be 0.1~10wt%.
12. composite polyester fiber as claimed in claim 1, it is characterised in that carbon nano-structured in the composite polyester fiber The content of compound be 0.5~7wt%.
13. composite polyester fiber as claimed in claim 1, it is characterised in that carbon nano-structured in the composite polyester fiber The content of compound be 1~5wt%.
14. composite polyester fiber as claimed in claim 1, it is characterised in that carbon nano-structured in the composite polyester fiber The content of compound be 2~4wt%.
15. composite polyester fiber as claimed in claim 1, it is characterised in that the carbon nano-structured compound is compound poly- The carbon nano-structured complex concentration of the sandwich layer of ester fiber is lower than the carbon nano-structured complex concentration of cortex.
16. composite polyester fiber as claimed in claim 1, it is characterised in that the carbon nano-structured compound has thickness Spend the cellular lamellar structure of hexatomic ring in below 100nm carbon.
17. composite polyester fiber as claimed in claim 1, it is characterised in that the carbon nano-structured compound has thickness Spend the cellular lamellar structure of hexatomic ring in below 20nm carbon.
18. composite polyester fiber as claimed in claim 1, it is characterised in that the carbon nano-structured compound has layer Number is any a kind or at least two kinds of of combination in the cellular lamellar structure of hexatomic ring of 1~10 layer of carbon.
19. composite polyester fiber as claimed in claim 1, it is characterised in that the carbon nano-structured compound be individual layer, Any a kind or at least two kinds of of combination in double-deck or 3~10 Rotating fields.
20. composite polyester fiber as claimed in claim 1, it is characterised in that carbon in the carbon nano-structured compound Microcosmic upper any a kind or at least two kinds of of the combination presented in warpage, curling, folded conformation of the cellular lamellar structure of hexatomic ring.
21. composite polyester fiber as claimed in claim 1, it is characterised in that in the carbon nano-structured compound, first Non-carbon nonoxygen element is adsorbed in carbon nanometer in the form of any a kind or at least two kinds of in simple substance, oxide or carbide of combination The surface or inside of structure.
22. composite polyester fiber as claimed in claim 1, it is characterised in that in the carbon nano-structured compound, first Non-carbon nonoxygen element is introduced by carbon source.
23. composite polyester fiber as claimed in claim 22, it is characterised in that the carbon source is selected from biomass carbon source, biology Any a kind or at least two kinds of of combination of the matter carbon source in plant and/or agriculture and forestry organic waste material.
24. composite polyester fiber as claimed in claim 22, it is characterised in that the carbon source is selected from needlebush, leaf wood, woods Any a kind or at least two kinds of of combination in Ye Mu, agriculture and forestry organic waste material.
25. composite polyester fiber as claimed in claim 23, it is characterised in that the agriculture and forestry organic waste material is selected from cornstalk, jade Any a kind in meter Xin, kaoliang stalk, megasse, bagasse, furfural dregs, xylose residue, wood chip, cotton stalk, shell and reed or extremely Few 2 kinds combination.
26. composite polyester fiber as claimed in claim 23, it is characterised in that the agriculture and forestry organic waste material is corncob.
27. a kind of preparation method of the composite polyester fiber containing graphene as described in one of claim 1~26, its feature exist In methods described is:
Carbon nano-structured compound is introduced during polyester in-situ polymerization, reaction finishes to obtain melt, melt discharging, pelletizing Complex polyester master batch is obtained, complex polyester master batch melt spinning, obtains the composite polyester fiber containing graphene.
28. method as claimed in claim 27, it is characterised in that the melt-spinning technology is preoriented yarn technique.
29. method as claimed in claim 28, it is characterised in that the wire vent temperature of the preoriented yarn is 30~70 DEG C, is gone out Silk humidity is 10~90%.
30. method as claimed in claim 28, it is characterised in that the wire vent temperature of the preoriented yarn is 55~65 DEG C, is gone out Silk humidity is 40~50%.
31. method as claimed in claim 28, it is characterised in that the wire vent temperature of the preoriented yarn is 62 DEG C, and wire vent is wet Spend for 42%.
32. method as claimed in claim 28, it is characterised in that the wire vent of the preoriented yarn uses air-cooled or water cooling.
33. method as claimed in claim 27, it is characterised in that the temperature of cooling water is 20~75 during the melt discharging ℃。
34. method as claimed in claim 27, it is characterised in that the temperature of cooling water is 40 DEG C during the melt discharging.
35. method as claimed in claim 27, it is characterised in that the draft speed of the melt discharging is 0.01~1m/s.
36. method as claimed in claim 27, it is characterised in that the carbon nano-structured compound is with carbon nano-structured The form of compound dry powder adds, or is added in the form of carbon nano-structured compound dispersion liquid.
37. method as claimed in claim 27, it is characterised in that the dispersant of the carbon nano-structured compound dispersion liquid Gather selected from deionized water, distilled water, ethanol, ethylene glycol, terephthalic acid (TPA), sodium acetate solution, DBSA, castor oil Any a kind or at least two kinds of of combination in oxygen vinethene.
38. method as claimed in claim 27, it is characterised in that in polyester fiber process, carbon nano-structured answers Compound adds any 1 of opportunity in raw material pulping stage, esterification prepolymerisation stage, precondensation stage, whole polycondensation phase Kind or at least two kinds of combinations.
39. method as claimed in claim 27, it is characterised in that in polyester fiber process, carbon nano-structured answers The addition opportunity of compound is the raw material pulping stage.
40. method as claimed in claim 27, it is characterised in that during the addition of the carbon nano-structured compound per kilogram Between be 30s~30min.
41. method as claimed in claim 27, it is characterised in that methods described comprises the following steps:
(1) reactor is put into after the mashing of polyacid, polyalcohol and carbon nano-structured compound is well mixed, is made in catalyst Under, polymerisation is completed in esterification and polycondensation, obtains melt;
(2) melt discharges under conditions of 20~75 DEG C of cooling waters, 0.01~1m/s draft speeds, is directly granulated and obtains master batch;
(3) by master batch at 30~70 DEG C of wire vent temperature, 10~90% wire vent damp conditions, using air-cooled or water cooling, melting is spun Silk, obtains the composite polyester fiber containing graphene.
42. method as claimed in claim 27, it is characterised in that the carbon nano-structured compound obtains by the following method :
(i) mixing biomass carbon source and catalyst, after stirring carries out catalytic treatment, it is dried to obtain presoma;
(ii) in protective atmosphere, by presoma 280~350 DEG C be incubated 1.5~2.5h, temperature programming afterwards to 950~ 1200 DEG C, 3~4h of insulation obtains crude product;The heating rate of described program heating is 15~20 DEG C/min;
(iii) after crude product is washed, carbon nano-structured compound is obtained.
43. method as claimed in claim 42, it is characterised in that the mass ratio of the biomass carbon source and catalyst is 1: 0.1~10.
44. method as claimed in claim 42, it is characterised in that the mass ratio of the biomass carbon source and catalyst is 1: 0.5~5.
45. method as claimed in claim 42, it is characterised in that the mass ratio of the biomass carbon source and catalyst is 1:1 ~3.
46. method as claimed in claim 42, it is characterised in that the catalyst be selected from the compound of manganese, iron containing compoundses, Any a kind or at least two kinds of of combination in cobalt compound and nickel compound containing;The iron containing compoundses are selected from the halogenated of iron Any a kind or at least two kinds of of combination in compound, the cyanide of iron and iron content hydrochlorate;The cobalt compound is selected from the halogen of cobalt Plain compound and containing any a kind or at least two kinds of of combination in cobaltatess;The nickel compound containing is selected from the chlorate of nickel and contained Any a kind or at least two kinds of of combination in nickelate.
47. method as claimed in claim 42, it is characterised in that the catalyst is selected from iron chloride, frerrous chloride, nitric acid Iron, ferrous nitrate, ferric sulfate, ferrous sulfate, the potassium ferricyanide, potassium ferrocyanide, three oxalic acid close potassium ferrite, cobalt chloride, cobalt nitrate, Any a kind or at least two kinds of of combination in cobaltous sulfate, cobalt acetate, nickel chloride, nickel nitrate, nickel sulfate and nickel acetate.
48. method as claimed in claim 42, it is characterised in that step (i) it is described stirring carry out catalytic treatment temperature be 150~200 DEG C, the time >=4h.
49. method as claimed in claim 42, it is characterised in that the time that step (i) stirring carries out catalytic treatment is 4 ~14h.
50. method as claimed in claim 42, it is characterised in that the moisture in the presoma is below 10wt%.
51. method as claimed in claim 42, it is characterised in that step (ii) described presoma is warming up to 280~350 DEG C Heating rate is 3~5 DEG C/min.
52. method as claimed in claim 42, it is characterised in that the protective atmosphere is appointing in nitrogen, helium, argon gas The combination of a kind or at least two kinds of of meaning.
53. method as claimed in claim 42, it is characterised in that the protective atmosphere is nitrogen.
54. method as claimed in claim 42, it is characterised in that step (iii) the crude product washing is the acid carried out successively Wash and wash, the temperature of the washing is 55~65 DEG C.
55. method as claimed in claim 54, it is characterised in that the pickling concentration is 3~6wt% hydrochloric acid.
56. method as claimed in claim 54, it is characterised in that the pickling concentration is 5wt% hydrochloric acid.
57. method as claimed in claim 54, it is characterised in that the washing uses deionized water and/or distilled water.
58. method as claimed in claim 54, it is characterised in that the temperature of the washing is 60 DEG C.
59. method as claimed in claim 42, it is characterised in that the biomass carbon source is cellulose and/or lignin.