CN1210334C - Sphere xylogen pearl body and clean preparation method for reverse phase suspension technology of program temp. raising and cross-linking solidifying - Google Patents
Sphere xylogen pearl body and clean preparation method for reverse phase suspension technology of program temp. raising and cross-linking solidifying Download PDFInfo
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Abstract
The present invention discloses a clean preparation method of spherical lignin bead bodies by a reverse-phase suspension technology of temperature programming and crosslinking solidification, which comprises the following steps: concentrated pulping paper-making black liquor or concentrated pulping paper-making red liquor is dispersed in unmixable solvents, namely dispersed phases; a dispersing agent, an activating agent and a crosslinking agent are added to prepare the spherical lignin bead bodies by crosslinking solidification under the action of an external force in the mode of temperature programming at ordinary pressure, the particle diameter distribution range of the spherical lignin bead bodies is from 1 to 50 mu m, from 50 to 100 mu m, from 100 to 300 mu m and from 300 to 1200 mu m, the average pore diameter is from 5 to 150 nm, the coefficient of uniformity is less than or equal to 1.30, the specific surface area is from 35 to 450 m<2>/g, the water ratio is from 50% to 75%, the stacking density is from 0.18 to 0.41 g/ml, and the stacking volume is from 2.44 to 5.56 ml/g. The present invention has the advantages of simple preparation process and nontoxicity. The products have a favorable chemical degradation resisting capability and a favorable biodegradation resisting capability.
Description
Technical field:
The invention belongs to functional high polymer material field, relate to globular lignin pearl body; Be particularly related to the recovery that cleans technology and solvent of globular lignin pearl body with specific function.
Background technology:
The world today, the deposit of oil, natural gas source is limited, and their research, development and utilization is on the rise to the influence that ball ecological environment brings, and this has impelled is that the macromolecular material of raw material is greatly developed with natural resource.Xylogen is very big in the quantity that occurring in nature exists, and always with the Mierocrystalline cellulose association, whole world terrestrial plant can produce 50,000,000,000 tons of xylogen every year, wherein the industrial lignin that produces in the cooking waste liquor of pulp and paper industry has 3,000 ten thousand tons.The history in existing several thousand of human use's Mierocrystalline cellulose, the xylogen that really begins one's study then has been the thing after nineteen thirty, and xylogen is not also well utilized so far, the xylogen of China only about 6% obtains utilizing.Xylogen owing to be not fully utilized, has become one of primary pollution source in the paper industry as the by product of wood saccharification industry and paper industry, and this not only causes serious environmental to pollute, and causes the significant waste of resource.The comprehensive utilization of the so-called xylogen in some paper mill also just is concentrated to finite concentration with sulfite waste lye, or with the sulfonation of alkaline cooking black liquor be concentrated to finite concentration, the user is given in dispersion agent and binding agent direct marketing as low grade, and added value is not high, and the enthusiasm of enterprise is not high yet.Therefore, how effectively to make good use of this renewable resources of xylogen, improve its added value, and the solution problem of environmental pollution becomes starting point of the present invention.
Contain hydroxyl, carboxyl, carbonyl isoreactivity functional group on the lignin molecule, therefore xylogen and derivative thereof have performances such as certain dispersion, bonding, chelating, can be used as the dispersion agent, cement setting retarder of the viscosity-depression agent mud in cement water reducing agent sandy soil stablizer, binding agent, the oil drilling etc., the emulsion stabilizer of pitch milk liquid etc.In light industry mainly as the strengthening agent of tensio-active agent, dyestuff, pigment, coating, printing ink, leather retanning agent and rubber item and coupling agent etc.Aspect water treatment, mainly can be used as flocculation agent, dispersion agent, Scale inhibitors, rust-preventive agent, inhibiter etc.If improve the performance of currently available products or produce product with higher economic benefit by chemical modification and other suitable approach, then will further widen the range of application of xylogen, and improve its added value, also improve simultaneously enterprise's comprehensive utilization xylogen and solve the enthusiasm that pulping back liquor pollutes, promote China's paper industry to continue, develop in a healthy way.
At present, the domestic and international then patent report of shape xylogen sorbent material preparation and applied research aspect if unsighted still.The globular lignin sorbent material can be controlled cell size, granularity, and advantage such as have that specific surface area is big, transparent performance and hydraulic performance are good, be easy to handle and suitable post on operate, and can be used to adsorb serum protein, separation and purification bacterial, preparation and separating chiral compound, purifying chloroplast DNA, adsorbing metal ions, separate transition metal ion and rare earth element, recovery noble metal etc.In addition, globular lignin pearl body is the carrier etc. of useful as drug solid phase synthesis also, so globular lignin pearl body and be that the globular lignin sorbent material that skeleton is developed will be with a wide range of applications with globular lignin pearl body.
The present invention is criterion with the cleaner production, adopt the reversed phase suspension technique of temperature programming and crosslinking curing to prepare globular lignin pearl body, for the development of globular lignin sorbent material provides base material, reclaim solvent (being disperse phase) then, and recovered solvent should be made the disperse phase that globular lignin pearl system is equipped with again, not only eliminated the environmental pollution of organic solvent, and reduced the production cost of globular lignin pearl body greatly, made the product of developing to realize industrialization.
Summary of the invention:
The object of the present invention is to provide the production method of the globular lignin pearl body of a series of different-grain diameters, promptly utilize spissated pulping back liquor or red liquid to be raw material, adopt the reversed phase suspension technique of temperature programming and crosslinking curing to prepare globular lignin pearl body and reclaim solvent, the whole process of preparation of globular lignin pearl body is the process of a crosslinking curing, and manufacturing process is simple, produces not have to poison, solvent is nontoxic, can reclaim, and non-environmental-pollution, be one clean, environmentally friendly technology.
The preparation technology of above-mentioned globular lignin pearl body comprises two steps: the anti-phase suspension of temperature programming and crosslinking curing and the recovery of solvent, and concrete technology is as follows:
The raw material and the prescription-massfraction of the anti-phase suspension step of temperature programming and crosslinking curing:
Spissated pulping back liquor or red liquid: 10～30%
Disperse phase: 50～79%
Dispersion agent: 0.1～5.0%
Activator: 0.5～10.0%
Linking agent: 0.5～15.0%
The anti-phase suspension processing step and the processing parameter of temperature programming and crosslinking curing: be equipped with condensation reflux unit and in establish in the reactor of automatic feeding device of constant temperature system and add spissated pulping back liquor or red liquid respectively, dispersion agent, solvent and activator etc., the external force effect is adopted and is stirred, after stirring, slowly drip linking agent, in 10～30min, dropwise, and rotating speed is controlled at 20-800r/min, temperature of reaction in the reinforced process is 5～65 ℃, add and expect that the back rises to 70～98 ℃ with the speed of 1～5 ℃/min with temperature, behind reaction 30～210min, reduce to normal temperature, total reaction times is 60-360min, can obtain the globular lignin pearl body of different-grain diameter 1-1200 μ m, this processing step can carry out under normal pressure.
The recovery of solvent
After utilizing filtration and sieve method with globular lignin pearl body and separated from solvent, solvent is carried out precipitate and separate to remove some insolubless under normal pressure, utilize extraction process to reclaim solvent then, solvent recovering yield is 90～100%.
In this technology, mainly from raw-material alkaline process or kraft process waste liquids such as Pinus massoniana Lamb, bamboo, bagasse, rice straw, reeds, its solid content is 5～65% to spissated pulping back liquor, and alkali lignin content is 2.5～35%; The red liquid of spissated pulping and paper-making is raw-material liquid waste of pulping by sulfite process from herbaceous plant such as needlebush, leaf wood and bagasses mainly, its solid content is 5～60%, the lignosulfonic acid salts contg is 1.5～35%, and wherein sulfonated lignin are mainly wooden quality sulphur acid Magnesium, calcium lignin sulphonate and sodium lignosulfonate etc.; Solvent is kerosene, transformation gasoline, paraffin oil, poly-alkylsiloxane, chlorobenzene etc., can select wherein one or more mixtures as required; Dispersion agent is an oleic acid, Arlacelc (English is translated into me and restrains), Arlacel60 (English is translated into me and restrains 160), Span20 (English is translated into class of department 20), Span40 (English is translated into class of department 40), Span60 (English is translated into class of department 60), Span80 (English is translated into class of department 80), sodium laurylsulfonate, Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, Tween20 (English is translated into polysorbas20), Tween 40 (English is translated into polysorbate40), Tween 60 (English is translated into polysorbate60), Tween 80 (English is translated into tween 80), Tween 85 (English is translated into polysorbate85), Tween 81 (English is translated into sorbimacrogol oleate100), Tween 61 (English is translated into tween 61), sodium oleate, tensio-active agent and Jian formula Tan Suan Magnesium such as potassium oleate, inorganic dispersant and gelatin such as calcium phosphate powder, polyvinyl alcohol, acid polyethylene, polyvinylpyrrolidone, organic polymer dispersion agents such as phenolic aldehyde and urea aldehyde polycondensate and sulfonated lignin, can select wherein one or more mixtures as required, when selecting two or more mixtures to mix, but its blending ratio arbitrary proportion, for tensio-active agent, should being controlled at of its HLB value is in 10～13 scopes, and the add-on of dispersion agent is 0.1%～5.0%; Activator is acidic substance such as alkaline matters such as sodium hydroxide, potassium hydroxide or hydrochloric acid, sulfuric acid, and add-on is 0.5～10.0%; Linking agent is formaldehyde and derivative thereof, comprising propenal, succinic aldehyde, melamine formaldehyde (MF), Paraformaldehyde 96 etc., and epoxy chloropropane, 1,3-two chloro-2-propyl alcohol, three isonitrile acid, add-on is 0.1～15.0%.
The present invention has the following advantages and positively effect:
1. utilize clean, environmentally friendly technology prepares globular lignin pearl body, and in the preparation process of pearl body, can reclaim solvent, reduce the production cost of globular lignin pearl body greatly, make the globular lignin pearl physical efficiency of developing realize industrialization, move towards market from the laboratory.
2. the high added value environmentfriendly products of developing-globular lignin pearl body, not only help transferring enterprise's comprehensive utilization xylogen and solve the enthusiasm that pulping back liquor pollutes, and widened the development approach of functional high molecule material and environmentfriendly products, promote the development of functional high molecule material and environmental protection industry.
3. develop the globular lignin pearl body of different-grain diameter, make it to be suitable for different purposes, as the removal and the hemanalysis of undesirable components in the blood, the separation and purification of various enzymes, the separation and purification of medicine, biochemical engineering material and usual protein etc.In addition, also can be used as stationary phase and the solid phase synthesis or the chipal compounds synthetic carrier of gel chromatography, affinity chromatography, and can be used for separating, identify, reclaiming precious metals such as inorganic metal ion and the uranium that from seawater, extracts, gold etc.
4. the reversed phase suspension technique of temperature programming and the crosslinking curing technology that cleans for preparing globular lignin pearl body has following advantage: the crosslinked and curing schedule of globular lignin pearl body is integrated, simplified schedule of operation; Method is simple to operate, to equipment require lowly, be easy to realize industrialization, granularity and porosity can artificially be controlled.
More than the raw material of each step and the massfraction summation of prescription be 100%.
Description of drawings:
Fig. 1 is a kind of process flow sheet according to the preparation method of globular lignin pearl body proposed by the invention.
Fig. 2 is that the particle diameter that utilizes XL30 ESEM type scanning electron microscope to take is the integral spherical electromicroscopic photograph and the configuration of surface electromicroscopic photograph thereof of the dry state globular lignin pearl body of 300～1200 μ m.
Embodiment:
The present invention is described in detail below in conjunction with accompanying drawing:
Embodiment 1: the processing step of present embodiment and order are as shown in Figure 1.Concrete steps are as follows:
The raw material of the anti-phase suspension step of temperature programming and crosslinking curing and prescription (unit-kilogram):
Pulping back liquor (Pinus massoniana Lamb alkali lignin solution, solid content 45%): 23.4 kilograms
Disperse phase (kerosene): 70.0 kilograms
Dispersion agent (Tween 80 and Span 80 mixtures, mass ratio is 1.7: 1): 0.4 kilogram
Activator (sodium hydroxide): 1.6 kilograms
Linking agent (epoxy chloropropane): 4.6 kilograms
The anti-phase suspension processing step and the processing parameter of temperature programming and crosslinking curing: be equipped with condensation reflux unit and in establish that to add solid content in the reactor of automatic feeding device of constant temperature system respectively be 45% pulping back liquor, be Pinus massoniana Lamb alkali lignin solution, dispersion agent, solvent and activator etc., after stirring, slowly drip linking agent, in 25min, dropwise, and rotating speed is controlled at 160r/min, temperature of reaction in the reinforced process is 15 ℃, add and expect that the back rises to 85 ℃ with the speed of 2 ℃/min with temperature, behind the reaction 120min, reduce to normal temperature, can obtain the globular lignin pearl body of different-grain diameter.This processing step can carry out under normal pressure.
(3) recovery of solvent
After utilizing filtration and sieve method with globular lignin pearl body and separated from solvent, solvent is carried out precipitate and separate to remove some insolubless under normal pressure, utilize extraction process to reclaim solvent then, solvent recovering yield can reach 98.5%.
Embodiment 2: the processing step of present embodiment and order are as shown in Figure 1.Concrete steps are as follows:
The raw material of the anti-phase suspension step of temperature programming and crosslinking curing and prescription (unit-kilogram):
Pulping back liquor (Pinus massoniana Lamb alkali lignin solution, solid content 65%): 12.0 kilograms
Disperse phase (transformer oil): 79.0 kilograms
Dispersion agent (Sodium dodecylbenzene sulfonate and polyvinyl alcohol mixture, mass ratio are 5: 1): 0.5 kilogram
Activator (sodium hydroxide): 2.0 kilograms
Linking agent (epoxy chloropropane): 6.5 kilograms
The anti-phase suspension processing step and the processing parameter of temperature programming and crosslinking curing: be equipped with condensation reflux unit and in establish that to add solid content in the reactor of automatic feeding device of constant temperature system respectively be 65% pulping back liquor, be Pinus massoniana Lamb alkali lignin solution, dispersion agent, solvent and activator etc., after stirring, slowly drip linking agent, in 30min, dropwise, and rotating speed is controlled at 500r/min, temperature of reaction in the reinforced process is 5 ℃, add and expect that the back rises to 95 ℃ with the speed of 5 ℃/min with temperature, behind the reaction 180min, reduce to normal temperature, can obtain the globular lignin pearl body of different-grain diameter.This processing step can carry out under normal pressure.
(3) recovery of solvent
After utilizing filtration and sieve method with globular lignin pearl body and separated from solvent, solvent is carried out precipitate and separate to remove some insolubless under normal pressure, utilize extraction process to reclaim solvent then, solvent recovering yield can reach 95%.
Embodiment 3: the processing step of present embodiment and order are as shown in Figure 1.Concrete steps are as follows:
The raw material of the anti-phase suspension step of temperature programming and crosslinking curing and prescription (unit-kilogram):
Pulping back liquor (Pinus massoniana Lamb alkali lignin solution, solid content 50%): 30.0 kilograms
Disperse phase (chlorobenzene): 56.5 kilograms
Dispersion agent (sodium lauryl sulphate, Span 80 and acid polyethylene, mass ratio are 1: 4: 1): 1.0 kilograms
Activator (sodium hydroxide): 4.0 kilograms
Linking agent (epoxy chloropropane): 8.5 kilograms
The anti-phase suspension processing step and the processing parameter of temperature programming and crosslinking curing: be equipped with condensation reflux unit and in establish that to add solid content in the reactor of automatic feeding device of constant temperature system respectively be 50% pulping back liquor, be Pinus massoniana Lamb alkali lignin solution, dispersion agent, solvent and activator etc., after stirring, slowly drip linking agent, in 30min, dropwise, and rotating speed is controlled at 700r/min, temperature of reaction in the reinforced process is 25 ℃, add and expect that the back rises to 90 ℃ with the speed of 3 ℃/min with temperature, behind the reaction 150min, reduce to normal temperature, can obtain the globular lignin pearl body of different-grain diameter.This processing step can carry out under normal pressure.
(3) recovery of solvent
After utilizing filtration and sieve method with globular lignin pearl body and separated from solvent, solvent is carried out precipitate and separate to remove some insolubless under normal pressure, utilize extraction process to reclaim solvent then, solvent recovering yield can reach 99.5%.
Embodiment 4: the processing step of present embodiment and order are as shown in Figure 1.Concrete steps are as follows:
The raw material of the anti-phase suspension step of temperature programming and crosslinking curing and prescription (unit-kilogram):
Pulping back liquor (Pinus massoniana Lamb alkali lignin solution, solid content 30%): 17.0 kilograms
Disperse phase (poly-alkylsiloxane): 69.0 kilograms
Dispersion agent (sodium oleate, Span 20 and gelatin mixture, mass ratio are 1.3: 1: 1): 0.7 kilogram
Activator (concentrated hydrochloric acid): 5.0 kilograms
Linking agent (formaldehyde): 8.3 kilograms
The anti-phase suspension processing step and the processing parameter of temperature programming and crosslinking curing: be equipped with condensation reflux unit and in establish that to add solid content in the reactor of automatic feeding device of constant temperature system respectively be 50% pulping back liquor, be Pinus massoniana Lamb alkali lignin solution, dispersion agent, solvent and activator etc., after stirring, slowly drip linking agent, in 20min, dropwise, and rotating speed is controlled at 150r/min, temperature of reaction in the reinforced process is 45 ℃, add and expect that the back rises to 98 ℃ with the speed of 2 ℃/min with temperature, behind the reaction 210min, reduce to normal temperature, can obtain the globular lignin pearl body of different-grain diameter.This processing step can carry out under normal pressure.
(3) recovery of solvent
After utilizing filtration and sieve method with globular lignin pearl body and separated from solvent, solvent is carried out precipitate and separate to remove some insolubless under normal pressure, utilize extraction process to reclaim solvent then, solvent recovering yield can reach 96.8%.
Embodiment 5: the processing step of present embodiment and order are as shown in Figure 1.
The raw material of the anti-phase suspension step of temperature programming and crosslinking curing and prescription (unit-kilogram):
Pulping back liquor (Pinus massoniana Lamb alkali lignin solution, solid content 45%): 26.2 kilograms
Disperse phase (kerosene): 60.0 kilograms
Dispersion agent (Tween85 and polyvinylpyrrolidone mixture, mass ratio are 9: 1): 0.5 kilogram
Activator (sodium hydroxide): 4.3 kilograms
Linking agent (epoxy chloropropane): 9.0 kilograms
The anti-phase suspension processing step and the processing parameter of temperature programming and crosslinking curing: be equipped with condensation reflux unit and in establish that to add solid content in the reactor of automatic feeding device of constant temperature system respectively be 45% pulping back liquor, be Pinus massoniana Lamb alkali lignin solution, dispersion agent, solvent and activator etc., after stirring, slowly drip linking agent, in 30min, dropwise, and rotating speed is controlled at 300r/min, temperature of reaction in the reinforced process is 65 ℃, add and expect that the back rises to 76 ℃ with the speed of 1 ℃/min with temperature, behind the reaction 180min, reduce to normal temperature, can obtain the globular lignin pearl body of different-grain diameter.This processing step can carry out under normal pressure.
(3) recovery of solvent
After utilizing filtration and sieve method with globular lignin pearl body and separated from solvent, solvent is carried out precipitate and separate to remove some insolubless under normal pressure, utilize extraction process to reclaim solvent then, solvent recovering yield can reach 100%.
Embodiment 6: the processing step of present embodiment and order are as shown in Figure 1.Concrete steps are as follows:
The raw material of the anti-phase suspension step of temperature programming and crosslinking curing and prescription (unit-kilogram):
Pulping back liquor (bamboo alkali lignin solution, solid content 47%): 20.0 kilograms
Disperse phase (transformer oil): 65.0 kilograms
Dispersion agent (Tween40, Span65 and calcium phosphate powder mixture, mass ratio are 2.8: 1: 3): 2.2 kilograms
Activator (sodium hydroxide): 2.8 kilograms
Linking agent (epoxy chloropropane): 10.0 kilograms
The anti-phase suspension processing step and the processing parameter of temperature programming and crosslinking curing: be equipped with condensation reflux unit and in establish that to add solid content in the reactor of automatic feeding device of constant temperature system respectively be 47% pulping back liquor, be bamboo alkali lignin solution, dispersion agent, solvent and activator etc., after stirring, slowly drip linking agent, in 30min, dropwise, and rotating speed is controlled at 120r/min, temperature of reaction in the reinforced process is 35 ℃, add and expect that the back rises to 90 ℃ with the speed of 5 ℃/min with temperature, behind the reaction 90min, reduce to normal temperature, can obtain the globular lignin pearl body of different-grain diameter.This processing step can carry out under normal pressure.
(3) recovery of solvent
After utilizing filtration and sieve method with globular lignin pearl body and separated from solvent, solvent is carried out precipitate and separate to remove some insolubless under normal pressure, utilize extraction process to reclaim solvent then, solvent recovering rate is 97.9%.
Embodiment 7: the processing step of present embodiment and order are as shown in Figure 1.Concrete steps are as follows:
The raw material of the anti-phase suspension step of temperature programming and crosslinking curing and prescription (unit-kilogram):
Pulping back liquor (rice straw alkali lignin solution, solid content 55%): 15.0 kilograms
Disperse phase (kerosene): 70.0 kilograms
Dispersion agent (Tween85 and Jian formula Tan Suan Magnesium mixture, mass ratio is 1: 9): 5.0 kilograms
Activator (potassium hydroxide): 3.0 kilograms
Linking agent (epoxy chloropropane): 7.0 kilograms
The anti-phase suspension processing step and the processing parameter of temperature programming and crosslinking curing: be equipped with condensation reflux unit and in establish that to add solid content in the reactor of automatic feeding device of constant temperature system respectively be 55% pulping back liquor, be rice straw alkali lignin solution, dispersion agent, solvent and activator etc., after stirring, slowly drip linking agent, in 30min, dropwise, and rotating speed is controlled at 400r/min, temperature of reaction in the reinforced process is 65 ℃, add and expect that the back rises to 80 ℃ with the speed of 2 ℃/min with temperature, behind the reaction 150min, reduce to normal temperature, can obtain the globular lignin pearl body of different-grain diameter.This processing step can carry out under normal pressure.
(3) recovery of solvent
After utilizing filtration and sieve method with globular lignin pearl body and separated from solvent, solvent is carried out precipitate and separate to remove some insolubless under normal pressure, utilize extraction process to reclaim solvent then, solvent recovering rate is 99.0%.
Embodiment 8: the processing step of present embodiment and order are as shown in Figure 1.Concrete steps are as follows:
The raw material of the anti-phase suspension step of temperature programming and crosslinking curing and prescription (unit-kilogram):
The red liquid of pulping and paper-making (Mu quality Huang Suan Magnesium solution, solid content 50%): 20.0 kilograms
Disperse phase (transformer oil): 60.0 kilograms
Dispersion agent (calcium phosphate powder and polyvinyl alcohol mixture, mass ratio are 1: 4): 3.0 kilograms
Activator (50% sulfuric acid): 10.0 kilograms
Linking agent (propenal): 7.0 kilograms
The anti-phase suspension processing step and the processing parameter of temperature programming and crosslinking curing: be equipped with condensation reflux unit and in establish that to add solid content in the reactor of automatic feeding device of constant temperature system respectively be 50% the red liquid of pulping and paper-making, be Mu quality Huang Suan Magnesium solution, dispersion agent, solvent and activator etc., after stirring, slowly drip linking agent, in 15min, dropwise, and rotating speed is controlled at 350r/min, temperature of reaction in the reinforced process is 40 ℃, add and expect that the back rises to 98 ℃ with the speed of 4 ℃/min with temperature, behind the reaction 210min, reduce to normal temperature, can obtain the globular lignin pearl body of different-grain diameter.This processing step can carry out under normal pressure.
(3) recovery of solvent
After utilizing filtration and sieve method with globular lignin pearl body and separated from solvent, solvent is carried out precipitate and separate to remove some insolubless under normal pressure, utilize extraction process to reclaim solvent then, solvent recovering rate is 93.0%.
Embodiment 9: the processing step of present embodiment and order are as shown in Figure 1.Concrete steps are as follows:
The raw material of the anti-phase suspension step of temperature programming and crosslinking curing and prescription (unit-kilogram):
The red liquid of pulping and paper-making (lignosulfonic acid sodium solution, solid content 50%): 15.0 kilograms
Disperse phase (paraffin oil): 60.0 kilograms
Dispersion agent (acid polyethylene and gelatin mixture, mass ratio are 1: 9): 4.0 kilograms
Activator (concentrated hydrochloric acid): 10.0 kilograms
Linking agent (melamine formaldehyde (MF)): 11.0 kilograms
The anti-phase suspension processing step and the processing parameter of temperature programming and crosslinking curing: be equipped with condensation reflux unit and in establish that to add solid content in the reactor of automatic feeding device of constant temperature system respectively be 50% the red liquid of pulping and paper-making, it is the lignosulfonic acid sodium solution, dispersion agent, solvent and activator etc., after stirring, slowly drip linking agent, in 25min, dropwise, and rotating speed is controlled at 80r/min, temperature of reaction in the reinforced process is 50 ℃, add and expect that the back rises to 95 ℃ with the speed of 2 ℃/min with temperature, behind the reaction 180min, reduce to normal temperature, can obtain the globular lignin pearl body of different-grain diameter.This processing step can carry out under normal pressure.
(3) recovery of solvent
After utilizing filtration and sieve method with globular lignin pearl body and separated from solvent, solvent is carried out precipitate and separate to remove some insolubless under normal pressure, utilize extraction process to reclaim solvent then, solvent recovering rate is 91.0%.
Embodiment 10: the processing step of present embodiment and order are as shown in Figure 1.Concrete steps are as follows:
The raw material of the anti-phase suspension step of temperature programming and crosslinking curing and prescription (unit-kilogram):
The red liquid of pulping and paper-making (calcium lignosulfonate solution, solid content 50%): 10.0 kilograms
Disperse phase (chlorobenzene): 50.0 kilograms
Dispersion agent (acid polyethylene, gelatin and urea aldehyde polycondensate mixture, mass ratio is 1: 2: 7): 5.0 kilograms
Activator (60% hydrochloric acid): 20.0 kilograms
Linking agent (Paraformaldehyde 96): 15.0 kilograms
The anti-phase suspension processing step and the processing parameter of temperature programming and crosslinking curing: be equipped with condensation reflux unit and in establish that to add solid content in the reactor of automatic feeding device of constant temperature system respectively be 50% the red liquid of pulping and paper-making, it is the lignosulfonic acid sodium solution, dispersion agent, solvent and activator etc., after stirring, slowly add linking agent, in 30min, dropwise, and rotating speed is controlled at 280r/min, temperature of reaction in the reinforced process is 65 ℃, add and expect that the back rises to 96 ℃ with the speed of 2 ℃/min with temperature, behind the reaction 210min, reduce to normal temperature, can obtain the globular lignin pearl body of different-grain diameter.This processing step can carry out under normal pressure.
(3) recovery of solvent
After utilizing filtration and sieve method with globular lignin pearl body and separated from solvent, solvent is carried out precipitate and separate to remove some insolubless under normal pressure, utilize extraction process to reclaim solvent then, solvent recovering rate is 92.0%.
Some physico-chemical properties of the globular lignin pearl body that the foregoing description makes see Table 1 to table 6:
The particle diameter of table 1 globular lignin pearl body and the relation of specific surface area
Pearl body particle diameter
1-50 50-100 100-300 300-1200
(μm)
Specific surface area
380±70 290±60 180±50 85.0±50
(m
2/g)
Table 2 particle diameter is the partial properties index of the globular lignin pearl body of 300-1200 μ m
Water ratio specific surface area mean pore size cell size tap density is piled up volume
Particle diameter (μ m)
(％) (m
2/g) (nm) (％) (g/ml) (ml/g)
300～1200 65～69 35～135 70～150 70～80 0.27～0.29 3.5～3.7
The acidproof ability of table 3 globular lignin pearl body
Acid concentration (mol/l) 0.5 1.0 2.0 4.0 6.0
Swelling ratio S (%) 0.00 2.00 3.15 4.00 5.56
Annotate: the globular lignin pearl body that with the particle diameter is 300-1200 μ m is a research object, and dwell temperature is 25 ℃, and time of repose is 24h.。
The alkaline-resisting ability of table 4 globular lignin pearl body
Alkali concn (mol/l) 0.5 1.0 2.0 4.0 6.0
Swelling ratio S (%) 8.33 11.11 15.15 15.33 19.88
Annotate: the globular lignin pearl body that with the particle diameter is 300-1200 μ m is a research object, and dwell temperature is 25 ℃, and time of repose is 24h.
The resistance of oxidation of table 5 globular lignin pearl body
Oxidization time
6.0 12.0 24.0 36.0 48.0 96.0
(h)
Mass loss
0.00 0.02 0.05 0.08 0.11 0.13
(％)
Annotate: the globular lignin pearl body that with the particle diameter is 300-1200 μ m is a research object, and oxidizing temperature is 65 ℃,
Oxygenant is 3.0%H
2O
2With 1m 0.12%FeSO
4
The antibiont degradation capability of table 6 globular lignin pearl body
Degradation time
10 30 60 90 120 150
(d)
Mass loss
0.07 0.13 0.21 0.49 0.76 1.23
(％)
Annotate: the globular lignin pearl body that with the particle diameter is 300-1200 μ m is a research object, and degradation temperature is 25 ℃.
Claims (8)
1. the method for preparing globular lignin pearl body of the reversed phase suspension technique of temperature programming and crosslinking curing is characterized in that:
The raw material and the prescription-massfraction of the anti-phase suspension step of temperature programming and crosslinking curing:
Spissated pulping back liquor or red liquid: 10～30%
Disperse phase: 50～79%
Dispersion agent: 0.1～5.0%
Activator: 0.5～10.0%
Linking agent: 0.5～15.0%
The anti-phase suspension processing step and the processing parameter of temperature programming and crosslinking curing: be equipped with condensation reflux unit and in establish in the reactor of automatic feeding device of constant temperature system and add spissated pulping back liquor or red liquid respectively, dispersion agent, solvent and activator etc., the external force effect is adopted and is stirred, after stirring, slowly drip linking agent, in 10～30min, dropwise, and rotating speed is controlled at 20-800r/min, temperature of reaction in the reinforced process is 5～65 ℃, add and expect that the back rises to 70～98 ℃ with the speed of 1～5 ℃/min with temperature, behind reaction 30～210min, reduce to normal temperature, total reaction times is 60-360min, can obtain the globular lignin pearl body of different-grain diameter 1-1200 μ m, this processing step carries out under normal pressure.
2. the method for preparing globular lignin pearl body of the reversed phase suspension technique of temperature programming according to claim 1 and crosslinking curing, after it is characterized in that utilizing under the normal pressure filtration and sieve method with globular lignin pearl body and separated from solvent, solvent is carried out precipitate and separate to remove some insolubless, utilize extraction process to reclaim solvent then.
3. the method for preparing globular lignin pearl body of the reversed phase suspension technique of temperature programming according to claim 1 and crosslinking curing, the spissated pulping back liquor that it is characterized in that adopting is mainly from Pinus massoniana Lamb, bamboo, bagasse, rice straw, the raw-material alkaline process of reed or kraft process waste liquid, its solid content is 5～65%, and alkali lignin content is 2.5～35%.
4. the method for preparing globular lignin pearl body of the reversed phase suspension technique of temperature programming according to claim 1 and crosslinking curing, it is characterized in that adopting the red liquid of spissated pulping and paper-making is raw-material liquid waste of pulping by sulfite process from needlebush, leaf wood and bagasse mainly, its solid content is 5～60%, and the lignosulfonic acid salts contg is 1.5～35%.
5. the method for preparing globular lignin pearl body of the reversed phase suspension technique of temperature programming according to claim 1 and crosslinking curing, it is characterized in that the disperse phase that uses be selected from kerosene, transformation gasoline, paraffin oil, poly-alkylsiloxane, the chlorobenzene one or both or two or more.
6. the method for preparing globular lignin pearl body of the reversed phase suspension technique of temperature programming according to claim 1 and crosslinking curing, it is characterized in that the dispersion agent that uses is selected from oleic acid, I restrains, I restrains 160, class of department 20, class of department 40, class of department 60, class of department 80, sodium laurylsulfonate, Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, polysorbas20, polysorbate40, polysorbate60, tween 80, polysorbate85, sorbimacrogol oleate100, tween 61, sulfonated castor oil, sodium oleate, potassium oleate tensio-active agent and magnesium basic carbonate, calcium phosphate powder inorganic dispersant and gelatin, polyvinyl alcohol, acid polyethylene, polyvinylpyrrolidone, one or both of phenolic aldehyde and urea aldehyde polycondensate and sulfonated lignin organic polymer dispersion agent or two or more, for tensio-active agent, should being controlled at of its HLB value is in 10～13 scopes, and the add-on of dispersion agent is 0.1%～5.0%.
7. the method for preparing globular lignin pearl body of the reversed phase suspension technique of temperature programming according to claim 1 and crosslinking curing, it is characterized in that the activator that uses is sodium hydroxide, potassium hydroxide alkalescence material or hydrochloric acid, sulfuric acid material, add-on is 0.5～10.0%.
8. the method for preparing globular lignin pearl body of the reversed phase suspension technique of temperature programming according to claim 1 and crosslinking curing, it is characterized in that linking agent is selected from formaldehyde, propenal, succinic aldehyde, melamine formaldehyde (MF), Paraformaldehyde 96, epoxy chloropropane, 1, one or both of 3-two chloro-2-propyl alcohol, three isonitrile acid or two or more, add-on is 0.5～15.0%.
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