CN103418353A - Absorbing material preparation method based on amination reinforced modified straw - Google Patents
Absorbing material preparation method based on amination reinforced modified straw Download PDFInfo
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Abstract
The invention relates to an absorbing material preparation method based on amination reinforced modified straw. Through the special design of the technological steps of straw raw material fermentation pre-processing, cation-type modification processing, anion-type modification processing, alkalization, crosslink preparing and the like and the special optimization of relative parameters, the absorbing material preparation method solves the technical problem that through the methods like single ion modification in the prior art, an absorbing material which meets the requirement of absorbing performance is difficult to obtain, and has the advantages that straw materials are good, the absorbing quantity is large, the absorbing speed is high, the technological process cost is low, the technological operation is simple and the method is applicable to industrialized production and cannot generate secondary pollution.
Description
Technical field
The present invention relates to the sorbing material technical field, relate in particular to a kind of preparation method of modified straw sorbing material, relate in particular a kind of preparation method who strengthens the modified straw sorbing material based on amination.
Background technology
At present, agricultural crop straw is the very high crop residues of fibre-bearing composition under left after seed results, comprising: the stalk of the various crop such as Cereal, beans, potato class, oil plant class, crudefiber crop and cotton, sugarcane, tobacco, melon and fruit.The stalk resource of China is very abundant, and at present only important crop material just has nearly 20 kinds, and output is huge.Except containing a large amount of carbon, also contain the elements such as potassium, silicon, nitrogen, calcium, magnesium, phosphorus in agricultural crop straw, and cellulose, hemicellulose, lignin, protein and amino acid etc.The composition that the stalk of Different Crop contains is had nothing in common with each other, as a whole, content of organic matter average out to 15.00% in stalk, average carbon containing 44.22%, nitrogen 0.62%, phosphorus 0.25%, potassium 1.44%, also have the elements such as magnesium, calcium, sulphur.
Agricultural crop straw is usually used in burning bavin, feed, makes compost etc. in traditional agriculture, occupies very important position in peasant family.Along with the raising of peasant planting enthusiasm and the steady volume increase of cereal crops in recent years, agricultural crop straw quantity is more and more many.But it is very few that the peasant understands the value of stalk, cause them to stalk, to carry out inappropriate processing, arbitrarily abandon and burn without control, it is the major way that stalk is disposed in the vast rural area of China, this not only can cause the damage of the wasting of resources, soil fertility, environmental pollution, also can cause taking place frequently of fire and traffic accident, and to human health and on every side vegeto-animal ecological environment cause serious harm; On the other hand, stalk is directly used in traditional application model of fertilizer, fuel and feed without any processing, just restricting the further raising of straw utilization rate, conversion ratio and economic benefit.
The straw utilization technical prospect is wide, and it will be the most considerable most economical energy that can develop 21 century.The annual grain annual production of China is in 500,000,000 t left and right, and cotton, oil plant Isoquant are at 3,000 ten thousand t, and the stalk total amount of these crops is more than 600,000,000 t.Wherein, 2.50 hundred million t stalks are for making fertile also field, and 0.48 hundred million t is for the raw material of industry, and 1.80 hundred million t, for life of farmers fuel, also have 1.20 hundred million t stalk residues, account for 20% of agricultural crop straw total amount.Therefore, wideling popularize agricultural crop straw and utilize new technology, stalk is turned waste into wealth, both can alleviate the pressure of rural area feed, fertilizer, fuel and the raw material of industry, is again an urgent demand of protecting Ecological Environment, promoting agriculture sustained coordination development.
China Patent Publication No. CN101638328A, open day is on February 3rd, 2010, a kind of stalk fertilizer and preparation method thereof is disclosed, this preparation method obtains fertilizer with the adsorbent fermented stalk of degrading straw, but the adsorbent incubation complexity of degrading straw, degradation process is easy to be subject to the impact of extraneous factor, and the method be not suitable for extensive Treating straw, the adsorbent cultivation of degrading straw needs the professional and technical personnel, culture environment is also had relatively high expectations, and is not suitable for promoting the use of in rural area.
The agricultural straw resource owning amount of China occupies first place in the world.The sown area of China's grain is about 1.13 hundred million hm
2, total output of grain 4.9 hundred million t, the grain straw total outputs such as corn, wheat are 500,000,000 t, add the stalk of other crops, more than annual production stalk 600,000,000 t.Although 2.5 hundred million t are for making fertile also field; 0.48 hundred million t are for the raw material of industry; 1.8 hundred million t are used for life of farmers fuel, but 1.2 hundred million t stalks residues are still arranged, this 20% stalk that accounts for total amount is stacked behind the house before peasant's room, becomes house refuse or burns in vain.Agricultural crop straw is first renewable resource on the earth, it is the significant by-products of crops, burning has caused the huge waste of resource, on the other hand, when burning, polluted air to emitting the harmful substances such as a large amount of sulfur dioxide, phenylpropyl alcohol pyrrole in air, endanger the healthy of people, affected the safety of traffic shipping, people's lives and properties and the normal growth of crops simultaneously.Remain in a large number the problems that are treated as the agricultural production saliency of stalks, become focus and the difficult point of government's care, social concerns, public opinion concern.
Along with scientific and technical development, the domestic exploitation to stalk at present have a great development, and its product relates to farmland fertilizer, animal feed, domestic life, construction material, industrial generation, chemical products, textile product etc.Visible, do the comprehensive utilization of agricultural crop straw well, turn waste into wealth, turn harm into good, be of great immediate significance and strategic importance.In these areas, the much advanced experience of the industrially developed country such as Japan, the U.S., Germany and processing method very worth we use for reference.But it is few to utilize it to improve agricultural soil preservation capacity of water and fertility report.
External mixed straw comprehensive utilization present situation: at present, produce wheat special soil stock amplification and capacity increase fertilizer to sorbing material about the mixing straw that utilizes corn, wheat, cotton abroad, the multifunctional comprehensive of turning waste into wealth utilizes technology, and the applicant have not been reported.
Domestic mixed straw comprehensive utilization present situation: in recent years, agricultural crop straw output is along with improving constantly of major product specific yield such as grains and increase sharply, according to the conservative principle, the applicant will adopt surveyed GVG than data, national stalk theoretical resources amount to be estimated.2006, the theoretical resources amount of the Primary Crop Straws such as national wheat, corn, paddy, rape and cotton was 4.33 hundred million tons.Wherein, wheat stalk is 7,600 ten thousand tons, and maize straw is 1.82 hundred million tons, and straw is 1.25 hundred million tons, and rape stalk is 1,300 ten thousand tons, and cotton stalk is 3,700 ten thousand tons.How to process these the recycling after superfluous mixed straw become the difficult problem in agricultural production process.Now the comprehensive utilization of mixed straw had to following several respects:
(1) stalk is made fuel: stalk is made fuel and still be take and directly burn as main, and unhygienic, energy utilization rate is only 13%.Gasification Technology occurred in recent years, and by stalk imperfect combustion or destructive distillation, obtained combustible gas and make fuel.What also have produces biogas by stalk by biofermentation and makes fuel.These conversion technology of biomass energies can improve 2 times-4 times of usings energy source.The rural area regenerative resource construction of attaching most importance to biogas, biomass energy; alleviated the situation of rural area energy supply shortage; changed the traditional pattern of lighting a fire and cooking in rural area; met the demand of peasant to high-grade energy; improved the life of farmers quality, adapted to the growth requirement in the new rural area of modernization, can consume a large amount of agricultural crop straws simultaneously; be a kind of mode that realizes the stalk treatment scale, but application at present seldom.
(2) stalk is made feed: contain higher crude fibre in stalk and limited microorganism and digestive ferment in the cud and, to the digestion of cell membrane Dissolve things inside, cause stalk palatability and trophism poor, can't by high efficiency animal absorb.Therefore, development and utilization straw feed resource, improve its utilization rate and nutritive value imperative.Stalk is processed through ensiling, ammonification, micro-storage, and the livestock and poultry of feeding promote the herding development to rise in value and increase income, and make stalk cross also field of abdomen.Space, potentiality that China utilizes agricultural crop straw to develop animal husbandry are also very large.Say technically at present, straw ensiling, ammonification and micro-storage technique comparative maturity, what need research is further to optimize feed preparation and the high variety of crops seed selection of the feeding rate of stalk.
(3) stalk is made fertilizer: stalk has following 3 kinds as the fertilizer method that also field utilizes:
1. stalk stack retting field (also claiming During High-Temperature Composting) also: the time that is characterized in long, affected by environment large, labour intensity is high, quantum of output is few, with low cost.Employing amount in rural area gradually reduces at present.
2. Mechanized Straw field also: mixed straw and mixed straw are through the mechanical crushing direct returning to farmland, that agricultural and agricultural machinery popularization department, for solving the project of utilizing problem to widely popularize of residue stalk, are characterized in that the mechanization of operation degree is high, the stalk processing time is short in recent years.But, because the peasant is familiar with not in placely, and straw-returning facility owning amount is relatively less, implements area and can implement area at a distance of very large.
3. utilize biochemical quick composting technology to manufacture the high-quality fertilizer: this is a kind of nineties in international 20th century of application of advanced biotechnology, uses sophisticated equipment and means production control process, straw is caused to the advanced method of high-quality biological organic fertilizer.The current new and high technology of utilizing, the optimal path of extensive, high efficiency production organic fertilizer.But exist production equipment introduction, digest and assimilate and DOMESTICATION PROBLEM.
(4) stalk is made base-material: at present, be mainly used in edible fungus culturing.Stalk kind mushroom is the good method that Treating straw is achieved many things at one stroke.Agricultural crop straw three major polymers: cellulose, hemicellulose and lignin three parts form.Organic principle in stalk be take cellulose and hemicellulose as main, is secondly lignin, protein, amino acid etc.Utilizing microorganism to take cellulose, to give birth to SCP as base starting material be one of method of utilizing now cellulose to have the most, does culture medium with agricultural crop straw and can plant the practical application that the multiple eating bacterium is exactly this principle.Facts have proved that every kilogram of stalk can produce white fungus, Asparagus, Hericium erinaceus or straw mushroom 0.25-0.4kg, flat mushroom 0.5-0.6kg, remarkable in economical benefits.
(5) stalk is made raw material: be mainly used in papermaking, also have on a small quantity for screen processed, cutlery box, clad plate, sound panel, insulation material, artificial carbon, active carbon etc.As industrial chemicals just still less, do 3% left and right that stalk amount that raw material consume only accounts for national output.
For China, be large agricultural country, agricultural crop straw output is large, distribution is wide, kind is many, is the precious resources of life of farmers and agricultural development for a long time always.Since reform and opening-up, under the Party Central Committee, the strong agriculture Huinong of State Council policy support, agricultural is scored consecutive bumper harvests, agricultural crop straw (hereinafter to be referred as " stalk ") generation increasing year by year.Add up according to investigations, within 2010, national stalk theoretical resources amount is 8.4 hundred million tons, can collect stock number and be about 700,000,000 tons.The stalk kind be take paddy rice, wheat, corn etc. as main.Wherein, approximately 2.11 hundred million tons of straw, approximately 1.54 hundred million tons of wheat straws, approximately 2.73 hundred million tons of corn stalk, approximately 2,600 ten thousand tons of cotton stalks, approximately 3,700 ten thousand tons of oil crops stalks (being mainly rape and peanut), approximately 2,800 ten thousand tons of beans stalks, approximately 2,300 ten thousand tons of potato class stalks.The grain-production of China is with obvious territorial characteristics, 13 grain main products such as Liaoning, Jilin, Heilungkiang, the Inner Mongol, Hebei, Henan, Hubei, Hunan, Shandong, Jiangsu, Anhui, Jiangxi, Sichuan are economized approximately 6.15 hundred million tons of (district) stalk theoretical resources amounts, account for 73% of national stalk theoretical resources amount.
China pays much attention to stalk comprehensive utilization work, and the stalk comprehensive utilization has obtained very fast development.It is still serious that but phenomenon is arbitrarily abandoned, burned to a lot of local stalks, brings series of environmental problems.Accelerate to advance the stalk comprehensive utilization, for stablizing the Agro-ecology balance, alleviate resource constraint, alleviate environmental pressure all tool be of great significance.
Heavy metal pollution refers to the environmental pollution caused by heavy metal or its compound.Heavy metal can not be biodegradable, and but can under the biological magnification of food chain, become the enrichment of thousands of times ground, finally enters human body.Although some heavy metal is the essential trace element of vital movement as manganese, copper, zinc etc., most of heavy metal is not that life is necessary.Surpass finite concentration, just will cause damage to health, cause various diseases, as: dehydration, stomachache, nauseating, dizzy, muscle dysfunction, children's nervous system destruction, lung pain, inflammatory eye, fash, vomiting, stomachache, pain, expiratory dyspnea, hepatic injury etc.
The method of removing the middle heavy metal ion of anhydrating is a lot, traditional have chemical precipitation method, oxidation-reduction method, ferrite process, electrolysis, evaporation concentration method, ion-exchange-resin process etc., but these methods exist mostly that investment is large, operating cost is high, operational administrative trouble and can produce secondary pollution and can not solve well the problems such as metal and water resource recycling.And biomass adsorbent has that adsorbance is large, adsorption rate is fast, cost is low, simple to operate, do not produce the advantages such as secondary pollution, more and more be subject to people's favor.
Summary of the invention
The objective of the invention is for above-mentioned deficiency, the inventor is on the basis of a large amount of existing documents, unique design by the performance to stalk and stalk modification, find above-mentioned document and general stalk modification absorbing process, such as methods such as single ionic modifications, be difficult to obtain the sorbing material that meets the absorption property requirement, and various stalk method of modifying and multiple conditional parameter exist possibility and the unpredictability of varied combination.The inventor is for the long-term technical barrier existed in the stalk modified technique, through long-term conscientious research, be surprisingly found out that, can reach after special combination of process steps is applied specific method Optimal Parameters that the extraordinary adsorbance of stalk material is large, adsorption rate is fast, the technological process cost is low, technological operation is simple, be applicable to suitability for industrialized production and do not produce the beneficial effect of secondary pollution.
For achieving the above object, the present invention is achieved by the following technical solutions:
A kind of preparation method who strengthens the modified straw sorbing material based on amination of the present invention, the described preparation method based on amination enhancing modified straw sorbing material comprises successively: stalk raw material fermentation pretreatment, above-mentioned cationic modified processing, anionic modification, alkalization and crosslinked preparation; It is characterized in that,
Described stalk raw material fermentation pretreatment: the agricultural crop straw of collection, first by being built-in with the stalk infrared high temperature shredding machine of correcting positioner in the same way, after carrying out repeatedly repeatedly in the same way the correcting location, then is become straw chopping to the stalk section of 0.73～0.76cm, and then smash to about 100-115 order by the pulverizer that is built-in with a plurality of spiral Disintegrating knifes is full and uniform, then the stalk powder of smashing is inserted in the sealing acidification pool, evenly pass into again the ether liquid that contains acetic acid in described sealing acidification pool, again described sealing acidification pool is boosted to 9.3～9.7MPa, temperature is from 35 ℃, evenly is warming up to gradually 125 ℃ with 7.5 ℃/minute, after keeping 35 minutes, pass into gradually again saturated vapor, then boost to 13.2～13.6MPa, wherein, described sealing acidification pool is conical, and sealing acidification pool inner bottom part central authorities evenly are provided with three double helix agitating rollers, and the stirring frequency of described double helix agitating roller is 75 rev/mins, then after the stalk after saturated vapor being processed is cleaned by deionized water, carry out abundant drying under 35～37 ℃ of low temperature, then dried powder of straw is minced, ammonium sulfate, dipotassium hydrogen phosphate, hydrolyzing straw with diluted acid pentose butanol fermentation waste water, soda ash is respectively according to weight portion: 23 parts: 5 parts: 7 parts: 36 parts: 2 parts, maintaining the temperature at 55～65 ℃ evenly mixes after 3～5 hours, it is inserted to 95 ℃ of quick-fried stills of constant temperature vapour is uniformly mixed, the quick-fried still internal vapor pressure of described constant temperature vapour is 16～19Mpa, keep this pressure dimension to press processing after 65～75min again with pressure in 0.0006MPa/ minute slow venting steam-explosion jar, after pressure in the venting steam-explosion jar, the above-mentioned stalk mixed solution uniformly mixed is fully fermented by two circulation coupled fermentation tanks, fermentation time is 55～65 minutes, wherein, the described pair of circulation coupled fermentation tank inner bottom part central authorities are equipped with single solid-state fermentation reactor, all around four inboards are equipped with four gas circulation machine/inner top middle positions and evenly are equipped with a plurality of active carbon adsorption rods, two of front and back gas circulation machines are connected by a breather line, and two of left and right gas circulation machine is connected by another breather line,
Described cationic modified processing: the mixed liquor after fully fermenting in above-mentioned stalk raw material fermentation pretreatment is evenly mixed 75～78 minutes according to the weight part ratio of 7:2:3:1:1 with 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride, Quaternium 24, alkylamide imidazoline quaternary ammonium salt, monoxone under 120 ℃; Again above-mentioned even mixing, after the stalk mixed treating liquid evaporate to dryness after 75～78 minutes, is added to the abundant stirring reaction 290～300min of the soda ash solution that is placed in 0.1～10g/L, wherein, described abundant stirring reaction temperature is 57 ℃, and bath raio is 1:50～1:53;
Described anionic modification: the stalk mixture after soda ash solution in above-mentioned cationic modified processing is processed evenly mixes 35～37 minutes according to the weight part ratio of 9:2:2:1 with epoxychloropropane, triethylamine or dimethylamine, laurate alkylolamides under 135 ℃; Again by above-mentioned even mixing after the stalk mixed treating liquid evaporate to dryness after 35～37 minutes, add the periodate solution that is placed in 0.1～10g/L to carry out lucifuge oxidation reaction 87～90min, wherein, described oxidizing reaction temperature is 65-70 ℃, bath raio 1:47～1:50; Then the stalk material after described oxidation reaction is placed in to 0.1mol/L glycerine solution and soaks 26～30min, until remove unreacted periodate fully, more fully wash by deionized water, naturally dry;
Described alkalization and crosslinked preparation: the stalk material after above-mentioned anionic modification is placed in to the soda ash cooking liquor, and alkali charge is 5～7%, and liquid-solid ratio is 1:6, carries out the boiling operation under 185 ℃; Boiling is complete dries afterwards with deionized water washing to neutral constant temperature; The stalk material again constant temperature dried is placed in 17～20% amine aqueous solution, after 70-80 ℃ of lower stirring reaction 130-180 min, with distilled water, cleans to neutrality, air-dry standby.
Wherein, in described alkalization and crosslinked preparation, the stalk material after above-mentioned anionic modification is placed in to the soda ash cooking liquor, alkali charge is 6%.
Wherein, in described alkalization and crosslinked preparation, boiling is complete dries afterwards with deionized water washing to neutral constant temperature; The stalk material again constant temperature dried is placed in 19% amine aqueous solution, after 77 ℃ of lower stirring reaction 156min, with distilled water, cleans to neutrality.
Beneficial effect: the present invention has transformed the determining of preparation method's technique that strengthens the modified straw sorbing material based on amination, creationaryly propose stalk raw material fermentations pretreatment, above-mentioned cationic modified processing, anionic modification, alkalization and crosslinked preparation, made stability, heat resistance, hot water resistance, uniformity and the persistence of the adsorption effect of the sorbing material after preparation all improve a lot.
The specific embodiment
Below in conjunction with the specific embodiment, further set forth the present invention.
Embodiment 1:
A kind of preparation method who strengthens the modified straw sorbing material based on amination, the described preparation method based on amination enhancing modified straw sorbing material comprises successively: stalk raw material fermentation pretreatment, above-mentioned cationic modified processing, anionic modification, alkalization and crosslinked preparation; It is characterized in that,
Described stalk raw material fermentation pretreatment: the agricultural crop straw of collection, first by being built-in with the stalk infrared high temperature shredding machine of correcting positioner in the same way, after carrying out repeatedly repeatedly in the same way the correcting location, then is become straw chopping to the stalk section of 0.73～0.76cm, and then smash to about 100-115 order by the pulverizer that is built-in with a plurality of spiral Disintegrating knifes is full and uniform, then the stalk powder of smashing is inserted in the sealing acidification pool, evenly pass into again the ether liquid that contains acetic acid in described sealing acidification pool, again described sealing acidification pool is boosted to 9.3～9.7MPa, temperature is from 35 ℃, evenly is warming up to gradually 125 ℃ with 7.5 ℃/minute, after keeping 35 minutes, pass into gradually again saturated vapor, then boost to 13.2～13.6MPa, wherein, described sealing acidification pool is conical, and sealing acidification pool inner bottom part central authorities evenly are provided with three double helix agitating rollers, and the stirring frequency of described double helix agitating roller is 75 rev/mins, then after the stalk after saturated vapor being processed is cleaned by deionized water, carry out abundant drying under 35～37 ℃ of low temperature, then dried powder of straw is minced, ammonium sulfate, dipotassium hydrogen phosphate, hydrolyzing straw with diluted acid pentose butanol fermentation waste water, soda ash is respectively according to weight portion: 23 parts: 5 parts: 7 parts: 36 parts: 2 parts, maintaining the temperature at 55～65 ℃ evenly mixes after 3～5 hours, it is inserted to 95 ℃ of quick-fried stills of constant temperature vapour is uniformly mixed, the quick-fried still internal vapor pressure of described constant temperature vapour is 16～19Mpa, keep this pressure dimension to press processing after 65～75min again with pressure in 0.0006MPa/ minute slow venting steam-explosion jar, after pressure in the venting steam-explosion jar, the above-mentioned stalk mixed solution uniformly mixed is fully fermented by two circulation coupled fermentation tanks, fermentation time is 55～65 minutes, wherein, the described pair of circulation coupled fermentation tank inner bottom part central authorities are equipped with single solid-state fermentation reactor, all around four inboards are equipped with four gas circulation machine/inner top middle positions and evenly are equipped with a plurality of active carbon adsorption rods, two of front and back gas circulation machines are connected by a breather line, and two of left and right gas circulation machine is connected by another breather line,
Described cationic modified processing: the mixed liquor after fully fermenting in above-mentioned stalk raw material fermentation pretreatment is evenly mixed 75～78 minutes according to the weight part ratio of 7:2:3:1:1 with 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride, Quaternium 24, alkylamide imidazoline quaternary ammonium salt, monoxone under 120 ℃; Again above-mentioned even mixing, after the stalk mixed treating liquid evaporate to dryness after 75～78 minutes, is added to the abundant stirring reaction 290～300min of the soda ash solution that is placed in 0.1～10g/L, wherein, described abundant stirring reaction temperature is 57 ℃, and bath raio is 1:50～1:53;
Described anionic modification: the stalk mixture after soda ash solution in above-mentioned cationic modified processing is processed evenly mixes 35～37 minutes according to the weight part ratio of 9:2:2:1 with epoxychloropropane, triethylamine or dimethylamine, laurate alkylolamides under 135 ℃; Again by above-mentioned even mixing after the stalk mixed treating liquid evaporate to dryness after 35～37 minutes, add the periodate solution that is placed in 0.1～10g/L to carry out lucifuge oxidation reaction 87～90min, wherein, described oxidizing reaction temperature is 65-70 ℃, bath raio 1:47～1:50; Then the stalk material after described oxidation reaction is placed in to 0.1mol/L glycerine solution and soaks 26～30min, until remove unreacted periodate fully, more fully wash by deionized water, naturally dry;
Described alkalization and crosslinked preparation: the stalk material after above-mentioned anionic modification is placed in to the soda ash cooking liquor, and alkali charge is 5～7%, and liquid-solid ratio is 1:6, carries out the boiling operation under 185 ℃; Boiling is complete dries afterwards with deionized water washing to neutral constant temperature; The stalk material again constant temperature dried is placed in 17～20% amine aqueous solution, after 70-80 ℃ of lower stirring reaction 130-180 min, with distilled water, cleans to neutrality, air-dry standby.
Embodiment 2:
A kind of preparation method who strengthens the modified straw sorbing material based on amination, the described preparation method based on amination enhancing modified straw sorbing material comprises successively: stalk raw material fermentation pretreatment, above-mentioned cationic modified processing, anionic modification, alkalization and crosslinked preparation; It is characterized in that,
Described stalk raw material fermentation pretreatment: the agricultural crop straw of collection, first by being built-in with the stalk infrared high temperature shredding machine of correcting positioner in the same way, after carrying out repeatedly repeatedly in the same way the correcting location, then is become straw chopping to the stalk section of 0.73～0.76cm, and then smash to about 100-115 order by the pulverizer that is built-in with a plurality of spiral Disintegrating knifes is full and uniform, then the stalk powder of smashing is inserted in the sealing acidification pool, evenly pass into again the ether liquid that contains acetic acid in described sealing acidification pool, again described sealing acidification pool is boosted to 9.3～9.7MPa, temperature is from 35 ℃, evenly is warming up to gradually 125 ℃ with 7.5 ℃/minute, after keeping 35 minutes, pass into gradually again saturated vapor, then boost to 13.2～13.6MPa, wherein, described sealing acidification pool is conical, and sealing acidification pool inner bottom part central authorities evenly are provided with three double helix agitating rollers, and the stirring frequency of described double helix agitating roller is 75 rev/mins, then after the stalk after saturated vapor being processed is cleaned by deionized water, carry out abundant drying under 35～37 ℃ of low temperature, then dried powder of straw is minced, ammonium sulfate, dipotassium hydrogen phosphate, hydrolyzing straw with diluted acid pentose butanol fermentation waste water, soda ash is respectively according to weight portion: 23 parts: 5 parts: 7 parts: 36 parts: 2 parts, maintaining the temperature at 55～65 ℃ evenly mixes after 3～5 hours, it is inserted to 95 ℃ of quick-fried stills of constant temperature vapour is uniformly mixed, the quick-fried still internal vapor pressure of described constant temperature vapour is 16～19Mpa, keep this pressure dimension to press processing after 65～75min again with pressure in 0.0006MPa/ minute slow venting steam-explosion jar, after pressure in the venting steam-explosion jar, the above-mentioned stalk mixed solution uniformly mixed is fully fermented by two circulation coupled fermentation tanks, fermentation time is 55～65 minutes, wherein, the described pair of circulation coupled fermentation tank inner bottom part central authorities are equipped with single solid-state fermentation reactor, all around four inboards are equipped with four gas circulation machine/inner top middle positions and evenly are equipped with a plurality of active carbon adsorption rods, two of front and back gas circulation machines are connected by a breather line, and two of left and right gas circulation machine is connected by another breather line,
Described cationic modified processing: the mixed liquor after fully fermenting in above-mentioned stalk raw material fermentation pretreatment is evenly mixed 75～78 minutes according to the weight part ratio of 7:2:3:1:1 with 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride, Quaternium 24, alkylamide imidazoline quaternary ammonium salt, monoxone under 120 ℃; Again above-mentioned even mixing, after the stalk mixed treating liquid evaporate to dryness after 75～78 minutes, is added to the abundant stirring reaction 290～300min of the soda ash solution that is placed in 0.1～10g/L, wherein, described abundant stirring reaction temperature is 57 ℃, and bath raio is 1:50～1:53;
Described anionic modification: the stalk mixture after soda ash solution in above-mentioned cationic modified processing is processed evenly mixes 35～37 minutes according to the weight part ratio of 9:2:2:1 with epoxychloropropane, triethylamine or dimethylamine, laurate alkylolamides under 135 ℃; Again by above-mentioned even mixing after the stalk mixed treating liquid evaporate to dryness after 35～37 minutes, add the periodate solution that is placed in 0.1～10g/L to carry out lucifuge oxidation reaction 87～90min, wherein, described oxidizing reaction temperature is 65-70 ℃, bath raio 1:47～1:50; Then the stalk material after described oxidation reaction is placed in to 0.1mol/L glycerine solution and soaks 26～30min, until remove unreacted periodate fully, more fully wash by deionized water, naturally dry;
Described alkalization and crosslinked preparation: the stalk material after above-mentioned anionic modification is placed in to the soda ash cooking liquor, and alkali charge is 6%, and liquid-solid ratio is 1:6, carries out the boiling operation under 185 ℃; Boiling is complete dries afterwards with deionized water washing to neutral constant temperature; The stalk material again constant temperature dried is placed in 17～20% amine aqueous solution, after 70-80 ℃ of lower stirring reaction 130-180 min, with distilled water, cleans to neutrality, air-dry standby.
Embodiment 3:
A kind of preparation method who strengthens the modified straw sorbing material based on amination, the described preparation method based on amination enhancing modified straw sorbing material comprises successively: stalk raw material fermentation pretreatment, above-mentioned cationic modified processing, anionic modification, alkalization and crosslinked preparation; It is characterized in that,
Described stalk raw material fermentation pretreatment: the agricultural crop straw of collection, first by being built-in with the stalk infrared high temperature shredding machine of correcting positioner in the same way, after carrying out repeatedly repeatedly in the same way the correcting location, then is become straw chopping to the stalk section of 0.73～0.76cm, and then smash to about 100-115 order by the pulverizer that is built-in with a plurality of spiral Disintegrating knifes is full and uniform, then the stalk powder of smashing is inserted in the sealing acidification pool, evenly pass into again the ether liquid that contains acetic acid in described sealing acidification pool, again described sealing acidification pool is boosted to 9.3～9.7MPa, temperature is from 35 ℃, evenly is warming up to gradually 125 ℃ with 7.5 ℃/minute, after keeping 35 minutes, pass into gradually again saturated vapor, then boost to 13.2～13.6MPa, wherein, described sealing acidification pool is conical, and sealing acidification pool inner bottom part central authorities evenly are provided with three double helix agitating rollers, and the stirring frequency of described double helix agitating roller is 75 rev/mins, then after the stalk after saturated vapor being processed is cleaned by deionized water, carry out abundant drying under 35～37 ℃ of low temperature, then dried powder of straw is minced, ammonium sulfate, dipotassium hydrogen phosphate, hydrolyzing straw with diluted acid pentose butanol fermentation waste water, soda ash is respectively according to weight portion: 23 parts: 5 parts: 7 parts: 36 parts: 2 parts, maintaining the temperature at 55～65 ℃ evenly mixes after 3～5 hours, it is inserted to 95 ℃ of quick-fried stills of constant temperature vapour is uniformly mixed, the quick-fried still internal vapor pressure of described constant temperature vapour is 16～19Mpa, keep this pressure dimension to press processing after 65～75min again with pressure in 0.0006MPa/ minute slow venting steam-explosion jar, after pressure in the venting steam-explosion jar, the above-mentioned stalk mixed solution uniformly mixed is fully fermented by two circulation coupled fermentation tanks, fermentation time is 55～65 minutes, wherein, the described pair of circulation coupled fermentation tank inner bottom part central authorities are equipped with single solid-state fermentation reactor, all around four inboards are equipped with four gas circulation machine/inner top middle positions and evenly are equipped with a plurality of active carbon adsorption rods, two of front and back gas circulation machines are connected by a breather line, and two of left and right gas circulation machine is connected by another breather line,
Described cationic modified processing: the mixed liquor after fully fermenting in above-mentioned stalk raw material fermentation pretreatment is evenly mixed 75～78 minutes according to the weight part ratio of 7:2:3:1:1 with 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride, Quaternium 24, alkylamide imidazoline quaternary ammonium salt, monoxone under 120 ℃; Again above-mentioned even mixing, after the stalk mixed treating liquid evaporate to dryness after 75～78 minutes, is added to the abundant stirring reaction 290～300min of the soda ash solution that is placed in 0.1～10g/L, wherein, described abundant stirring reaction temperature is 57 ℃, and bath raio is 1:50～1:53;
Described anionic modification: the stalk mixture after soda ash solution in above-mentioned cationic modified processing is processed evenly mixes 35～37 minutes according to the weight part ratio of 9:2:2:1 with epoxychloropropane, triethylamine or dimethylamine, laurate alkylolamides under 135 ℃; Again by above-mentioned even mixing after the stalk mixed treating liquid evaporate to dryness after 35～37 minutes, add the periodate solution that is placed in 0.1～10g/L to carry out lucifuge oxidation reaction 87～90min, wherein, described oxidizing reaction temperature is 65-70 ℃, bath raio 1:47～1:50; Then the stalk material after described oxidation reaction is placed in to 0.1mol/L glycerine solution and soaks 26～30min, until remove unreacted periodate fully, more fully wash by deionized water, naturally dry;
Described alkalization and crosslinked preparation: the stalk material after above-mentioned anionic modification is placed in to the soda ash cooking liquor, and alkali charge is 6%, and liquid-solid ratio is 1:6, carries out the boiling operation under 185 ℃; Boiling is complete dries afterwards with deionized water washing to neutral constant temperature; The stalk material again constant temperature dried is placed in 19% amine aqueous solution, after 70-80 ℃ of lower stirring reaction 130-180 min, with distilled water, cleans to neutrality, air-dry standby.
Embodiment 4:
A kind of preparation method who strengthens the modified straw sorbing material based on amination, the described preparation method based on amination enhancing modified straw sorbing material comprises successively: stalk raw material fermentation pretreatment, above-mentioned cationic modified processing, anionic modification, alkalization and crosslinked preparation; It is characterized in that,
Described stalk raw material fermentation pretreatment: the agricultural crop straw of collection, first by being built-in with the stalk infrared high temperature shredding machine of correcting positioner in the same way, after carrying out repeatedly repeatedly in the same way the correcting location, then is become straw chopping to the stalk section of 0.73～0.76cm, and then smash to about 100-115 order by the pulverizer that is built-in with a plurality of spiral Disintegrating knifes is full and uniform, then the stalk powder of smashing is inserted in the sealing acidification pool, evenly pass into again the ether liquid that contains acetic acid in described sealing acidification pool, again described sealing acidification pool is boosted to 9.6MPa, temperature is from 35 ℃, evenly is warming up to gradually 125 ℃ with 7.5 ℃/minute, after keeping 35 minutes, pass into gradually again saturated vapor, then boost to 13.2～13.6MPa, wherein, described sealing acidification pool is conical, and sealing acidification pool inner bottom part central authorities evenly are provided with three double helix agitating rollers, and the stirring frequency of described double helix agitating roller is 75 rev/mins, then after the stalk after saturated vapor being processed is cleaned by deionized water, carry out abundant drying under 35～37 ℃ of low temperature, then dried powder of straw is minced, ammonium sulfate, dipotassium hydrogen phosphate, hydrolyzing straw with diluted acid pentose butanol fermentation waste water, soda ash is respectively according to weight portion: 23 parts: 5 parts: 7 parts: 36 parts: 2 parts, maintaining the temperature at 59 ℃ evenly mixes after 3～5 hours, it is inserted to 95 ℃ of quick-fried stills of constant temperature vapour is uniformly mixed, the quick-fried still internal vapor pressure of described constant temperature vapour is 16～19Mpa, keep this pressure dimension to press processing after 65～75min again with pressure in 0.0006MPa/ minute slow venting steam-explosion jar, after pressure in the venting steam-explosion jar, the above-mentioned stalk mixed solution uniformly mixed is fully fermented by two circulation coupled fermentation tanks, fermentation time is 55～65 minutes, wherein, the described pair of circulation coupled fermentation tank inner bottom part central authorities are equipped with single solid-state fermentation reactor, all around four inboards are equipped with four gas circulation machine/inner top middle positions and evenly are equipped with a plurality of active carbon adsorption rods, two of front and back gas circulation machines are connected by a breather line, and two of left and right gas circulation machine is connected by another breather line,
Described cationic modified processing: the mixed liquor after fully fermenting in above-mentioned stalk raw material fermentation pretreatment is evenly mixed 75～78 minutes according to the weight part ratio of 7:2:3:1:1 with 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride, Quaternium 24, alkylamide imidazoline quaternary ammonium salt, monoxone under 120 ℃; Again above-mentioned even mixing, after the stalk mixed treating liquid evaporate to dryness after 75～78 minutes, is added to the abundant stirring reaction 290～300min of the soda ash solution that is placed in 0.1～10g/L, wherein, described abundant stirring reaction temperature is 57 ℃, and bath raio is 1:50～1:53;
Described anionic modification: the stalk mixture after soda ash solution in above-mentioned cationic modified processing is processed evenly mixes 35～37 minutes according to the weight part ratio of 9:2:2:1 with epoxychloropropane, triethylamine or dimethylamine, laurate alkylolamides under 135 ℃; Again by above-mentioned even mixing after the stalk mixed treating liquid evaporate to dryness after 35～37 minutes, add the periodate solution that is placed in 0.1～10g/L to carry out lucifuge oxidation reaction 87～90min, wherein, described oxidizing reaction temperature is 65-70 ℃, bath raio 1:47～1:50; Then the stalk material after described oxidation reaction is placed in to 0.1mol/L glycerine solution and soaks 26～30min, until remove unreacted periodate fully, more fully wash by deionized water, naturally dry;
Described alkalization and crosslinked preparation: the stalk material after above-mentioned anionic modification is placed in to the soda ash cooking liquor, and alkali charge is 6%, and liquid-solid ratio is 1:6, carries out the boiling operation under 185 ℃; Boiling is complete dries afterwards with deionized water washing to neutral constant temperature; The stalk material again constant temperature dried is placed in 19% amine aqueous solution, after 70-80 ℃ of lower stirring reaction 130-180 min, with distilled water, cleans to neutrality, air-dry standby.
The present invention is not limited to above-mentioned specific embodiment, is not deviating under spirit of the present invention and real situation thereof, and those of ordinary skill in the art can make according to the present invention various corresponding changes and distortion.Within these corresponding changes and distortion all should belong to the protection domain of claims of the present invention.
Claims (3)
1. a preparation method who strengthens the modified straw sorbing material based on amination, the described preparation method who strengthens the modified straw sorbing material based on amination comprises successively: stalk raw material fermentation pretreatment, above-mentioned cationic modified processing, anionic modification, alkalization and crosslinked preparation; It is characterized in that,
Described stalk raw material fermentation pretreatment: the agricultural crop straw of collection, first by being built-in with the stalk infrared high temperature shredding machine of correcting positioner in the same way, after carrying out repeatedly repeatedly in the same way the correcting location, then is become straw chopping to the stalk section of 0.73～0.76cm, and then smash to about 100-115 order by the pulverizer that is built-in with a plurality of spiral Disintegrating knifes is full and uniform, then the stalk powder of smashing is inserted in the sealing acidification pool, evenly pass into again the ether liquid that contains acetic acid in described sealing acidification pool, again described sealing acidification pool is boosted to 9.3～9.7MPa, temperature is from 35 ℃, evenly is warming up to gradually 125 ℃ with 7.5 ℃/minute, after keeping 35 minutes, pass into gradually again saturated vapor, then boost to 13.2～13.6MPa, wherein, described sealing acidification pool is conical, and sealing acidification pool inner bottom part central authorities evenly are provided with three double helix agitating rollers, and the stirring frequency of described double helix agitating roller is 75 rev/mins, then after the stalk after saturated vapor being processed is cleaned by deionized water, carry out abundant drying under 35～37 ℃ of low temperature, then dried powder of straw is minced, ammonium sulfate, dipotassium hydrogen phosphate, hydrolyzing straw with diluted acid pentose butanol fermentation waste water, soda ash is respectively according to weight portion: 23 parts: 5 parts: 7 parts: 36 parts: 2 parts, maintaining the temperature at 55～65 ℃ evenly mixes after 3～5 hours, it is inserted to 95 ℃ of quick-fried stills of constant temperature vapour is uniformly mixed, the quick-fried still internal vapor pressure of described constant temperature vapour is 16～19Mpa, keep this pressure dimension to press processing after 65～75min again with pressure in 0.0006MPa/ minute slow venting steam-explosion jar, after pressure in the venting steam-explosion jar, the above-mentioned stalk mixed solution uniformly mixed is fully fermented by two circulation coupled fermentation tanks, fermentation time is 55～65 minutes, wherein, the described pair of circulation coupled fermentation tank inner bottom part central authorities are equipped with single solid-state fermentation reactor, all around four inboards are equipped with four gas circulation machine/inner top middle positions and evenly are equipped with a plurality of active carbon adsorption rods, two of front and back gas circulation machines are connected by a breather line, and two of left and right gas circulation machine is connected by another breather line,
Described cationic modified processing: the mixed liquor after fully fermenting in above-mentioned stalk raw material fermentation pretreatment is evenly mixed 75～78 minutes according to the weight part ratio of 7:2:3:1:1 with 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride, Quaternium 24, alkylamide imidazoline quaternary ammonium salt, monoxone under 120 ℃; Again above-mentioned even mixing, after the stalk mixed treating liquid evaporate to dryness after 75～78 minutes, is added to the abundant stirring reaction 290～300min of the soda ash solution that is placed in 0.1～10g/L, wherein, described abundant stirring reaction temperature is 57 ℃, and bath raio is 1:50～1:53;
Described anionic modification: the stalk mixture after soda ash solution in above-mentioned cationic modified processing is processed evenly mixes 35～37 minutes according to the weight part ratio of 9:2:2:1 with epoxychloropropane, triethylamine or dimethylamine, laurate alkylolamides under 135 ℃; Again by above-mentioned even mixing after the stalk mixed treating liquid evaporate to dryness after 35～37 minutes, add the periodate solution that is placed in 0.1～10g/L to carry out lucifuge oxidation reaction 87～90min, wherein, described oxidizing reaction temperature is 65-70 ℃, bath raio 1:47～1:50; Then the stalk material after described oxidation reaction is placed in to 0.1mol/L glycerine solution and soaks 26～30min, until remove unreacted periodate fully, more fully wash by deionized water, naturally dry;
Described alkalization and crosslinked preparation: the stalk material after above-mentioned anionic modification is placed in to the soda ash cooking liquor, and alkali charge is 5～7%, and liquid-solid ratio is 1:6, carries out the boiling operation under 185 ℃; Boiling is complete dries afterwards with deionized water washing to neutral constant temperature; The stalk material again constant temperature dried is placed in 17～20% amine aqueous solution, after 70-80 ℃ of lower stirring reaction 130-180 min, with distilled water, cleans to neutrality, air-dry standby.
2. the preparation method who strengthens the modified straw sorbing material based on amination according to claim 1, it is characterized in that: wherein, in described alkalization and crosslinked preparation, the stalk material after above-mentioned anionic modification is placed in to the soda ash cooking liquor, alkali charge is 6%.
3. according to claim 1 or the 2 or 3 described preparation methods that strengthen the modified straw sorbing material based on amination, it is characterized in that: wherein, in described alkalization and crosslinked preparation, boiling is complete dries afterwards with deionized water washing to neutral constant temperature; The stalk material again constant temperature dried is placed in 19% amine aqueous solution, after 77 ℃ of lower stirring reaction 156 min, with distilled water, cleans to neutrality.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104289198A (en) * | 2014-10-22 | 2015-01-21 | 苏州正业昌智能科技有限公司 | Composite material and preparation method thereof |
| CN104289197A (en) * | 2014-10-22 | 2015-01-21 | 苏州正业昌智能科技有限公司 | Amination-enhanced modified straw based composite material and preparation method thereof |
| CN105193846A (en) * | 2015-09-01 | 2015-12-30 | 福建龙生生物科技有限公司 | Application of nano graphene oxide |
| CN105214621A (en) * | 2015-10-13 | 2016-01-06 | 山东省环境保护科学研究设计院 | A kind of preparation method of novel straw cellulose adsorbent |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0857028A (en) * | 1994-08-25 | 1996-03-05 | Shohei Hoshino | Deodorant |
| CN101961645A (en) * | 2010-10-14 | 2011-02-02 | 华南理工大学 | Adsorbing agent for eliminating S4O2<-> in acid mine wastewater and preparation method thereof |
| CN102423693A (en) * | 2011-08-26 | 2012-04-25 | 四川大学 | Preparation and application methods of sulfur dioxide rice straw adsorbent |
| CN102600804A (en) * | 2012-03-26 | 2012-07-25 | 西安科技大学 | Method of using crop straw to produce acidic wastewater adsorbent for mine |
| CN102626608A (en) * | 2012-04-16 | 2012-08-08 | 南京大学 | Straw modified into amphiprotic adsorbent and preparation method thereof |
-
2013
- 2013-09-02 CN CN201310391613.8A patent/CN103418353B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0857028A (en) * | 1994-08-25 | 1996-03-05 | Shohei Hoshino | Deodorant |
| CN101961645A (en) * | 2010-10-14 | 2011-02-02 | 华南理工大学 | Adsorbing agent for eliminating S4O2<-> in acid mine wastewater and preparation method thereof |
| CN102423693A (en) * | 2011-08-26 | 2012-04-25 | 四川大学 | Preparation and application methods of sulfur dioxide rice straw adsorbent |
| CN102600804A (en) * | 2012-03-26 | 2012-07-25 | 西安科技大学 | Method of using crop straw to produce acidic wastewater adsorbent for mine |
| CN102626608A (en) * | 2012-04-16 | 2012-08-08 | 南京大学 | Straw modified into amphiprotic adsorbent and preparation method thereof |
Cited By (11)
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|---|---|---|---|---|
| CN104289198A (en) * | 2014-10-22 | 2015-01-21 | 苏州正业昌智能科技有限公司 | Composite material and preparation method thereof |
| CN104289197A (en) * | 2014-10-22 | 2015-01-21 | 苏州正业昌智能科技有限公司 | Amination-enhanced modified straw based composite material and preparation method thereof |
| CN104289197B (en) * | 2014-10-22 | 2016-04-06 | 苏州正业昌智能科技有限公司 | A kind of amination strengthens modified straw based composites and preparation method thereof |
| CN105193846A (en) * | 2015-09-01 | 2015-12-30 | 福建龙生生物科技有限公司 | Application of nano graphene oxide |
| CN105329972A (en) * | 2015-09-30 | 2016-02-17 | 太仓碧奇新材料研发有限公司 | Straw composite material preparation method |
| CN105214621A (en) * | 2015-10-13 | 2016-01-06 | 山东省环境保护科学研究设计院 | A kind of preparation method of novel straw cellulose adsorbent |
| CN108905972A (en) * | 2018-07-23 | 2018-11-30 | 成都清境环境科技有限公司 | A kind of adsorbent for heavy metal and its preparation method and application |
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| CN108905971B (en) * | 2018-07-23 | 2021-01-26 | 厦门量研新材料科技有限公司 | High-valence metal ion adsorbent and preparation method and application thereof |
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| CN114950376A (en) * | 2022-06-09 | 2022-08-30 | 兰州大学 | Modified straw anion adsorption material and preparation method and application thereof |
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