CN103756683B - A kind of hillside soil-solidified-agent and preparation method thereof - Google Patents
A kind of hillside soil-solidified-agent and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of hillside soil-solidified-agent, alkali paper-making Heisui River or cooking waste liquor is mainly utilized to be raw material, add formaldehyde, phenol and alkali etc., under alkalescence, carry out condensation reaction with formaldehyde, phenol etc. by the xylogen in papermaking black and generate dark red liquid, collect the starch wastewater in factory in addition, successively carry out being oxidized, gelatinization reaction, and carry out crosslinked and denaturing treatment, generate modified starch, then the resol mixed solution of dark red liquid and generation is mixed and made into hillside soil-solidified-agent.The solid soil of this soil-solidified-agent environmental protection is effective, can resist the erosion of rainwater and wind-force, can also improve firmness and the weatherability of soil, and the water-retentivity of sand bed during soil uphill can be improved.The invention also discloses the preparation method of above-mentioned hillside soil-solidified-agent.
Description
Technical field
The invention belongs to soil-solidified-agent technical field, be specifically related to a kind of hillside soil-solidified-agent and preparation method thereof.
Background technology
Industrial, carrying out utilizing vegetable fibre, in paper-making process, a large amount of waste water from cookings being produced, not only to environment, also causing certain wasting of resources.In these waste water, main component is xylogen, accounts for 28% ~ 33% of its solid substance; Equally, washing in the starch course of processing, press filtration, the process section such as concentrated can produce a lot of organic liquid wastes too, cause the pollution of environment, containing deliquescent organism such as starch, protein, carbohydrate, carbohydrate, fat, amino acid in these waste liquids, wherein starch content is maximum, accounts for 35% ~ 60% of waste liquid; By the pollution that the discharge that not only can reduce waste water after starch waste liquor Appropriate application causes, effectively can also promote the recycling of resource simultaneously.
Hillside soil is chiltern, poor water retention property, and soil property is loose, and hillside plant growing survives rate variance.At present, the solidifying agent for administering sandy soil in technology has flyash, polyacrylamide, high molecular polymer etc., and wherein the solidifying agent such as flyash, polyacrylamide effect is comparatively single, length consuming time, and sand-fixing effect is not remarkable; And synthesising macromolecule copolymer solidifying agent complex procedures, cost is higher, has potential risk of environmental pollution, limits promoting the use of of it.
Summary of the invention
The object of the present invention is to provide a kind of hillside soil-solidified-agent, the solid soil of this soil-solidified-agent environmental protection is effective, the erosion of rainwater and wind-force can be resisted, firmness and the weatherability of soil can also be improved, and the water-retentivity of sand bed during soil uphill can be improved.
The present invention also aims to the preparation method that above-mentioned hillside soil-solidified-agent is provided, this preparation method rationally can recycle the starch waste liquor in the black liquor in plant alkaline process or cooking waste liquor and the starch course of processing, the discharge of decreasing pollution thing, effective recycle can be carried out to resource, realize turning waste into wealth; And technique is simple, cost is low.
First object of the present invention is achieved by the following technical measures: a kind of hillside soil-solidified-agent, prepares by the following method:
(1) black liquor in plant alkaline process or cooking waste liquor is chosen, concentrated, obtain concentrated solution;
(2) in concentrated solution, add phenol and formaldehyde, make xylogen in black liquor or cooking waste liquor and formaldehyde, phenol reactant at alkaline condition, generate dark red liquid;
(3) starch waste liquor is chosen, oxygenant is added in starch waste liquor, through oxide treatment, obtain Sumstar 190 waste liquid, in Sumstar 190 waste liquid, add paste agent, through gelatinization process, obtain pasted starch, in pasted starch, add linking agent, obtain cross-linking starch, in cross-linking starch, add sanitas carry out rotproofing, make modified starch;
(4) modified starch obtained in dark red liquid obtained in step (2) and step (3) is mixed, i.e. obtained hillside soil-solidified-agent.
The present invention, from environmental angle, by transforming the recovery of the starch waste liquor in the black liquor in plant alkaline process or cooking waste liquor and the starch course of processing, achieving the second stage employ of refuse, decreasing the discharge of pollutent, defining the recycle of resource.
The organic liquid waste in industrial production selected by solidifying agent in the present invention, reduce manufacturing cost, can improve the physico-chemical property of soil and improve the water retention capacity of soil, this solidifying agent main component is the organism such as starch, xylogen, easy decomposition, can not work the mischief to environment.
Described in step of the present invention (1), the solid content of concentrated solution is preferably more than 10%.Concentrate and can adopt evaporation concentration mode.
In step of the present invention (2) in phenol and concentrated solution xylogen be 7 ~ 9g:20 ~ 25g with magnitude relation, in formaldehyde and concentrated solution, xylogen is 20mL ~ 25mL:20 ~ 25g with magnitude relation, and in alkali and concentrated solution, xylogen is 4 ~ 5g:20 ~ 25g with magnitude relation; Alkali can adopt sodium hydroxide, potassium hydroxide etc.
Step of the present invention adds phenol and formaldehyde in (2) in concentrated solution, makes black liquor or cooking waste liquor and formaldehyde, phenol reactant at alkaline condition, and generate dark red liquid, the reaction related in this process mainly contains following several:
A () in the basic conditions, phenol and formaldehyde condensation reaction generate formaldehyde phenolic resin;
B (), using alkali if sodium hydroxide or potassium hydroxide etc. are as catalyzer, the xylogen in black liquor or cooking waste liquor and formaldehyde produce condensation reaction, generate xylogen-resol.
C the xylogen in () black liquor or cooking waste liquor and phenol carry out condensation reaction, generate xylogen-phenol condensate, make the phenolic hydroxyl group of xylogen, thus the active hydrogen provided on more multi-aromatic ring, improve the reactive behavior of xylogen, enhance the reaction of itself and formaldehyde, finally generate xylogen-phenol-formaldehyde condensate.
So the dark red liquid in the present invention, is mainly the mixing solutions of formaldehyde phenolic resin, xylogen-resol and xylogen-phenol-formaldehyde condensate.
Preferably regulate in step of the present invention (2) that temperature is 75 ~ 90 DEG C, pH value is 9 ~ 10 make black liquor or cooking waste liquor and formaldehyde, phenol carry out water-bath 2.5 ~ 3h.
The solid content of the starch waste liquor described in step of the present invention (3) is preferably 15 ~ 20%.
The oxygenant adopted during oxide treatment in step of the present invention (3) to be mass percentage be 25% chlorine bleach liquor or concentration be the persulfate aqueous solution of 0.3 ~ 0.8g/mL, described chlorine bleach liquor or persulfate aqueous solution and starch waste liquor be 3 ~ 8mL:50mL with magnitude relation, oxide treatment is carry out 40 ~ 80min in the water-bath of 25 ~ 34 DEG C in temperature, be oxidizing to starch solution color gradually flexible thoroughly, Sumstar 190 waste liquid.
Time wherein clorox or Potassium Persulphate add, preferably slowly add, limit edged stirs, and makes starch waste liquor oxidizing reaction abundant.
Step of the present invention adds paste agent in (3) in Sumstar 190 waste liquid, and paste agent is aqueous sodium hydroxide solution, and its mass percentage is 28 ~ 32%, and the pH value regulating Sumstar 190 waste liquid is 9 ~ 10, carries out gelatinization reaction 50 ~ 60min, obtains pasted starch.
Preferably add several times when wherein paste agent adds, be preferably and add at twice, centre arranges certain time interval, and preferably interval is about half hour interpolation once.
First add after the water accounting for pasted starch cumulative volume 0.5 ~ 1 times carries out agitation and dilution in step of the present invention (3) in pasted starch, then add linking agent in pasted starch, linking agent and pasted starch be 1 ~ 5mL:50mL with magnitude relation; Described linking agent is preferably borax solution, and the concentration of described borax solution is preferably 0.09 ~ 0.11g/mL.
In cross-linking starch, add the sanitas of employing when sanitas carries out rotproofing in step of the present invention (3) is Whitfield's ointment, and the amount ratio of Whitfield's ointment and cross-linking starch is 3 ~ 8g:100mL.
When wherein carrying out rotproofing, preferred rapid stirring is evenly incubated about 1 hour afterwards, makes translucent viscous liquid, is modified starch.
The volume ratio of the dark red liquid described in step of the present invention (4) and described modified starch is preferably 2 ~ 3:5.
The present invention mainly utilizes alkali paper-making Heisui River or cooking waste liquor to be raw material, add formaldehyde, phenol and alkali according to a certain percentage, under alkalescence, carry out condensation reaction with formaldehyde, phenol etc. by the xylogen in papermaking black and produce wooden quality class resol, collect the starch wastewater in factory in addition, by successively carrying out with clorox, sodium hydroxide being oxidized, gelatinization reacts, and using borax as linking agent, add Whitfield's ointment, mix, final generation modified starch, then itself and the resol mixed solution generated are mixed and made into hillside soil-solidified-agent.
Second object of the present invention is achieved by the following technical measures: the preparation method of above-mentioned hillside soil-solidified-agent, containing following steps:
(1) black liquor in plant alkaline process or cooking waste liquor is chosen, concentrated, obtain concentrated solution;
(2) in concentrated solution, add phenol and formaldehyde, make xylogen in black liquor or cooking waste liquor and formaldehyde, phenol reactant at alkaline condition, generate dark red liquid;
(3) starch waste liquor is chosen, oxygenant is added in starch waste liquor, through oxide treatment, obtain Sumstar 190 waste liquid, in Sumstar 190 waste liquid, add paste agent, through gelatinization process, obtain pasted starch, in pasted starch, add linking agent, obtain cross-linking starch, in cross-linking starch, add sanitas carry out rotproofing, make modified starch;
(4) modified starch obtained in dark red liquid obtained in step (2) and step (3) is mixed, i.e. obtained hillside soil-solidified-agent.
Compared with prior art, tool of the present invention has the following advantages:
(1) the hillside soil-solidified-agent in the present invention, the solid soil of this soil-solidified-agent environmental protection is effective, can resist the erosion of rainwater and wind-force, can also improve firmness and the weatherability of soil, and the water-retentivity of sand bed during soil uphill can be improved;
(2) the hillside soil-solidified-agent in the present invention rationally can be recycled the starch waste liquor in the black liquor in plant alkaline process or cooking waste liquor and the starch course of processing, the discharge of decreasing pollution thing, effective recycle can be carried out to resource, realize turning waste into wealth;
(3) material for the manufacture of hillside solidifying agent in the present invention is nutritious, cheap, and organic content is more than 80%, easily be degraded to soil ulmin and contain some elements required for growth and development of plants, can soil be improved, increase fertility, be beneficial to the growth of plant.
Embodiment
The present invention is described in further detail for the embodiment provided below in conjunction with contriver, the raw material below adopted and reagent, as indicated without special, is commercially available.
first part: hillside soil-solidified-agent and preparation method thereof
embodiment 1
The hillside soil-solidified-agent that the present embodiment provides, prepares by the following method:
(1) by black liquor (cooking waste liquor) evaporation concentration that extracts in plant alkaline process to its solid substance >=10%;
(2) concentrated black liquor is added the amount of phenol, formaldehyde, sodium hydroxide by the content setting of wherein xylogen, make xylogen: phenol: the mass ratio of sodium hydroxide is 23:7:4, in formaldehyde and concentrated solution, xylogen is 20mL:25g with magnitude relation;
(3) concentrated black liquor, phenol, formaldehyde, sodium hydroxide mixing are added in Erlenmeyer flask, be placed in isothermal reaction on water-bath, control temperature is 75 ~ 90 DEG C, pH is 9 ~ 10, after about 3h, reaction terminates, and obtain dark red liquid, this dark red liquid is the mixed solution of resol, xylogen-phenol-formaldehyde condensate;
The reaction related in this process has:
A () in the basic conditions, phenol and formaldehyde condensation reaction generate formaldehyde phenolic resin;
B (), using alkali if sodium hydroxide is as catalyzer, in black liquor, xylogen and formaldehyde produce condensation reaction, generate lignin phenolic resin;
C () in the basic conditions, xylogen and phenol carry out condensation reaction, generate xylogen-phenol condensate, make the phenolic hydroxyl group of xylogen, thus the active hydrogen provided on more multi-aromatic ring, improve the reactive behavior of xylogen, enhance the reaction of itself and formaldehyde, finally generate xylogen-phenol-formaldehyde condensate.
(4) get 100mL starch waste liquor and regulate its solid content to 15 ~ 20%, put into Erlenmeyer flask, be placed on 25 DEG C of water-baths;
(5) get chlorine bleach liquor 6 ~ 16mL that mass percentage is 25%, slowly add in the starch waste liquor of Erlenmeyer flask, limit edged stirs, and allows its oxidizing reaction fully to look bleach;
(6) after about 30min, divide and add the sodium hydroxide solution (about adding once half an hour) that mass concentration is 30% for 2 times, and the pH value controlling reaction solution is 9.5, carry out the gelatinization reaction of about 1h, obtain pasted starch;
(7) in pasted starch, add a small amount of water and carry out agitation and dilution, the consumption of water is 0.5 times of pasted starch cumulative volume, get the borax soln of 0.1g/mL as linking agent, linking agent and pasted starch be 2mL:50mL with magnitude relation, and the Whitfield's ointment adding dissolving is as sanitas, obtain modified starch, wherein the amount ratio of Whitfield's ointment and cross-linking starch is 3g:100mL;
(8) be added in modified starch solution by dark red liquid and mix, wherein the amount ratio of dark red liquid and modified starch is 2mL:5mL, is hillside soil-solidified-agent.
embodiment 2
The hillside soil-solidified-agent that the present embodiment provides, prepares by the following method:
(1) by black liquor (cooking waste liquor) evaporation concentration that extracts in plant alkaline process to its solid substance >=10%;
(2) concentrated black liquor is added the amount of phenol, formaldehyde, sodium hydroxide by the content setting of wherein xylogen, make xylogen: phenol: the mass ratio of potassium hydroxide is 25:9:5, in formaldehyde and concentrated solution, xylogen is 25mL:25g with magnitude relation;
(3) concentrated black liquor, phenol, formaldehyde, sodium hydroxide mixing are added in Erlenmeyer flask, be placed in isothermal reaction on water-bath, control temperature is 80 DEG C, pH is 9.5, after about 2.5h, reaction terminates, and obtain dark red liquid, this dark red liquid is the mixed solution of resol, xylogen-phenol-formaldehyde condensate;
The reaction related in this process has:
A () in the basic conditions, phenol and formaldehyde condensation reaction generate formaldehyde phenolic resin;
B (), using alkali if sodium hydroxide is as catalyzer, in black liquor, xylogen and formaldehyde produce condensation reaction, generate lignin phenolic resin;
C () in the basic conditions, xylogen and phenol carry out condensation reaction, generate xylogen-phenol condensate, make the phenolic hydroxyl group of xylogen, thus the active hydrogen provided on more multi-aromatic ring, improve the reactive behavior of xylogen, enhance the reaction of itself and formaldehyde, finally generate xylogen-phenol-formaldehyde condensate.
(4) getting the adjustment of 100mL starch waste liquor is 15% ~ 20% emulsus in solid content, puts into Erlenmeyer flask, is placed on about 30 DEG C of water-baths;
(5) in the basic conditions, get 6 ~ 16mL concentration be the Potassium Persulphate of 0.5g/mL as oxygenant, be slowly added in the 100mL starch waste liquor in Erlenmeyer flask, be slowly stirred to color transparent gradually;
(6) after about 30min, add the sodium hydroxide solution that mass concentration is 30% per half an hour, regulate pH to 9 ~ 10, carry out 2 times respectively, carry out the gelatinization reaction of about 1h, obtain pasted starch;
(7) in pasted starch, add a small amount of water and carry out agitation and dilution, the consumption of water accounts for pasted starch cumulative volume 1 times, get the borax soln of 0.1g/mL as linking agent, linking agent and pasted starch be 5mL:50mL with magnitude relation, and with a small amount of water dissolution Whitfield's ointment, add as sanitas, obtained modified starch solution, the amount ratio of Whitfield's ointment and cross-linking starch is 5g:100mL;
(8) be added in modified starch solution by dark red liquid and mix, wherein the amount ratio of dark red liquid and modified starch solution is than being 3mL:5mL, is hillside soil-solidified-agent.
second section: the application of hillside soil-solidified-agent
application Example one: Gu native effect experimental
Hillside soil surface is evenly sprayed to by after solidifying agent dilution 5-8 times in embodiment 1, every square metre sprays the hardener dose after dilution is 80 ~ 150mL, through 2 ~ 3d natural air drying, the tack coat that 2 ~ 3cm is thick can be formed, then measure soil compactibility and water-retentivity; The solidifying agent stoste of synthesizing with this formula is fixed the sand, and soil layer firmness can reach 33.56kg/cm
3, be do not carry out 4 times of solid soil (when fixing the sand, soil layer firmness is 8.67kg/cm
3), the water conservation time length was increased to 47 days by 19 days.
application Example two: weathering tests
Adopted the soil layer of the hillside soil-solidified-agent in embodiment 1 by spraying and do not use the soil layer of hillside soil-solidified-agent to contrast the weathering tests carried out 2 months, period simulated rainfall 5 times, carry out when 10 to December, this, north wind was large in period, wind-force 4-6 level, through Experimental comparison, draws the soil using hillside soil-solidified-agent, before and after weathering, the change of sand bed flintiness is little, and firmness is about from 32.89kg/cm
3drop to 24.63kg/cm
3, illustrate that solid soil is respond well, the erosion of rainwater and wind-force can be resisted.
So, use the sand bed after the solid soil of the hillside soil-solidified-agent in the present invention not only can improve firmness and the weatherability of soil, Gu soil is respond well, the erosion of rainwater and wind-force can be resisted
,the water-retentivity of sand bed can also be improved.
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from spirit of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included in protection scope of the present invention.
Claims (9)
1. a hillside soil-solidified-agent, is characterized in that preparing by the following method:
(1) black liquor in plant alkaline process or cooking waste liquor is chosen, concentrated, obtain concentrated solution;
(2) in concentrated solution, add phenol and formaldehyde, make xylogen in black liquor or cooking waste liquor and formaldehyde, phenol reactant at alkaline condition, generate dark red liquid;
(3) starch waste liquor is chosen, oxygenant is added in starch waste liquor, through oxide treatment, obtain Sumstar 190 waste liquid, in Sumstar 190 waste liquid, add paste agent, through gelatinization process, obtain pasted starch, in pasted starch, add linking agent, obtain cross-linking starch, in cross-linking starch, add sanitas carry out rotproofing, make modified starch;
(4) modified starch obtained in dark red liquid obtained in step (2) and step (3) is mixed, i.e. obtained hillside soil-solidified-agent.
2. according to the hillside soil-solidified-agent described in claim 1, it is characterized in that: described in step (1), the solid content of concentrated solution is more than 10%.
3. according to the hillside soil-solidified-agent described in claim 1, it is characterized in that: in step (2) in phenol and concentrated solution xylogen be 7 ~ 9g:20 ~ 25g with magnitude relation, in formaldehyde and concentrated solution, xylogen is 20mL ~ 25mL:20 ~ 25g with magnitude relation, and in alkali and concentrated solution, xylogen is 4 ~ 5g:20 ~ 25g with magnitude relation.
4. according to the hillside soil-solidified-agent described in claim 1, it is characterized in that: regulate that temperature is 75 ~ 90 DEG C in step (2), pH value is 9 ~ 10 make black liquor or cooking waste liquor and formaldehyde, phenol carry out water-bath 2.5 ~ 3h.
5. according to the hillside soil-solidified-agent described in claim 1, it is characterized in that: the solid content of the starch waste liquor described in step (3) is 15 ~ 20%.
6. according to the hillside soil-solidified-agent described in claim 1, it is characterized in that: the oxygenant adopted during oxide treatment in step (3) to be mass percentage be 25% chlorine bleach liquor or concentration be the persulfate aqueous solution of 0.3 ~ 0.8g/mL, described chlorine bleach liquor or persulfate aqueous solution and starch waste liquor be 3 ~ 8mL:50mL with magnitude relation, oxide treatment is carry out 40 ~ 80min in the water-bath of 25 ~ 34 DEG C in temperature, be oxidizing to starch solution color gradually flexible thoroughly, Sumstar 190 waste liquid.
7. according to the hillside soil-solidified-agent described in claim 1, it is characterized in that: step adds paste agent in (3) in Sumstar 190 waste liquid, paste agent is aqueous sodium hydroxide solution, its mass percentage is 28% ~ 32%, the pH value regulating Sumstar 190 waste liquid is 9 ~ 10, carry out gelatinization reaction 50 ~ 60min, obtain pasted starch.
8. according to the hillside soil-solidified-agent described in claim 1, it is characterized in that: the volume ratio of the dark red liquid described in step (4) and described modified starch is 2 ~ 3:5.
9. the preparation method of the hillside soil-solidified-agent described in any one of claim 1-8, is characterized in that containing following steps:
(1) black liquor in plant alkaline process or cooking waste liquor is chosen, concentrated, obtain concentrated solution;
(2) in concentrated solution, add phenol and formaldehyde, make xylogen in black liquor or cooking waste liquor and formaldehyde, phenol reactant at alkaline condition, generate dark red liquid;
(3) starch waste liquor is chosen, oxygenant is added in starch waste liquor, through oxide treatment, obtain Sumstar 190 waste liquid, in Sumstar 190 waste liquid, add paste agent, through gelatinization process, obtain pasted starch, in pasted starch, add linking agent, obtain cross-linking starch, in cross-linking starch, add sanitas carry out rotproofing, make modified starch;
(4) modified starch obtained in dark red liquid obtained in step (2) and step (3) is mixed, i.e. obtained hillside soil-solidified-agent.
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| CN104005249B (en) * | 2014-05-22 | 2016-06-08 | 云南省轻工业科学研究院 | A kind of preparation method of paper grade (stock) mixed aid |
| CN104861985B (en) * | 2015-06-11 | 2018-04-20 | 延边大学 | Organic environmental-protection sand-consolidating agent and preparation method |
| CN105693966B (en) * | 2016-03-21 | 2018-01-12 | 北京林业大学 | A kind of preparation method of pyrolysis oil Lauxite sand-consolidating agent |
| CZ2017406A3 (en) * | 2017-07-14 | 2019-01-23 | Maneko, Spol. S R.O. | Reclamation of sandy soils under difficult climatic conditions |
| CN110195372B (en) * | 2019-06-19 | 2021-03-30 | 东南生态修复有限公司 | Wood fiber production method |
| CN111575010A (en) * | 2020-04-10 | 2020-08-25 | 陕西省交通建设集团公司 | Soil curing agent capable of improving drying shrinkage performance of reinforced soil and preparation method thereof |
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| CN102952548A (en) * | 2011-08-30 | 2013-03-06 | 张保良 | Method for preparing wind-prevention and sand-fixation water retaining agent by use of pulping and papermaking waste liquid |
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Address after: 510000 Guangdong, Guangzhou, Zhongshan, No. 1, Yuexiu District Road, No. 34, No. 3 Patentee after: HUAYUAN LANDSCAPE ARCHITECTURE CO., LTD. Address before: 510600, No. 34, No. three, Zhongshan Road, Yuexiu District, Guangdong, Guangzhou Patentee before: Guangzhou Huayuan Landscaping Co.,Ltd. |