CN109678382B - Preparation method and application of ester ether sulfonated composite water reducing agent based on straw modification - Google Patents

Preparation method and application of ester ether sulfonated composite water reducing agent based on straw modification Download PDF

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CN109678382B
CN109678382B CN201910130401.1A CN201910130401A CN109678382B CN 109678382 B CN109678382 B CN 109678382B CN 201910130401 A CN201910130401 A CN 201910130401A CN 109678382 B CN109678382 B CN 109678382B
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straw
acid
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storage tank
hydrolysis
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CN109678382A (en
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章德玉
张惠琴
张建斌
刘流
王鹏
刘岿
司长代
王小芳
刘新文
雷新有
吕玲玲
李志锋
郭峰
赵爱英
朱元成
左国防
唐慧安
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Tianshui Normal University
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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    • C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
    • C08H8/00—Macromolecular compounds derived from lignocellulosic materials
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
    • C04B2103/302—Water reducers

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Abstract

The invention discloses a preparation method and application of an ester ether sulfonated composite water reducing agent based on straw modification. The straw hydrolysis powder is obtained by hydrolyzing crop straws after preliminary crushing, cleaning, drying, fine crushing and micro crushing pretreatment. According to the invention, the crop straw raw material is smashed and hydrolyzed, the straw lignin and cellulose are firstly subjected to step-by-step sulfonation modification to form sulfonate, and then the lignocellulose is subjected to cellulose esterification modification to obtain the straw-based ester ether sulfonated composite water reducing agent, so that the problem that the water reducing rate of the straw-based water reducing agent is relatively low by 10-15% is solved, the obtained water reducing agent can be directly used under the conditions that the water reducing rate is about 25% and the retardation time is moderate, and the process is continuous and compact, easy to operate, low in cost, precipitation-proof and easy to industrialize.

Description

Preparation method and application of ester ether sulfonated composite water reducing agent based on straw modification
Technical Field
The invention relates to a biomass-based water reducing agent prepared by modifying crop straws, and in particular relates to a preparation method and application of an ester ether sulfonated type composite water reducing agent based on straw modification.
Background
At present, along with the increasing shortage of petrochemical raw materials required by a new generation of high-performance petroleum-based polycarboxylate water reducer for preparing a concrete admixture, the outstanding problem of price rise all the way is caused, the rapid development of the new generation of high-performance polycarboxylate water reducer is restricted, the production cost of the polycarboxylate water reducer is continuously increased, and the polycarboxylate water reducer with higher performance advantages than water reducers such as naphthalene series, aliphatic series, sulfamate series, lignin series and the like cannot be widely popularized and applied in the building industry. Researchers at home and abroad begin to research the water reducing agent with low cost and high performance in recent years. The water reducing agent is an important concrete admixture, is widely applied to China at present and comprises a lignosulfonate water reducing agent and a naphthalene water reducing agent, and the two water reducing agents have a plurality of defects, so that the development of a new water reducing agent variety is imperative. Meanwhile, the development of the water reducing agent industry in China faces problems of performance improvement, cost reduction, environmental friendliness and the like. With the improvement of environmental protection standards, some processes including naphthalene water reducers and the like are gradually eliminated, and the popularization and application prospects of the high-performance polycarboxylic acid water reducer in China are not optimistic due to the price factor of the high-performance polycarboxylic acid water reducer. Therefore, the research and development of the novel high-efficiency water reducing agent which is environment-friendly, has up-to-standard performance and meets the economic development level of China becomes an important research subject.
The research on the low-cost polycarboxylate water reducer is mainly embodied in that biomass-based renewable raw materials are used as a main method for reducing the polycarboxylate water reducer, the application of modified cellulose, hemicellulose, starch, monosaccharide and the like in the water reducer is mainly reported at present, and the modification methods mainly comprise sulfonation, esterification, etherification, amidation and the like.
Crop straws are inexpensive biomass raw materials which cannot be fully utilized, and comprise the rest parts of wheat, rice, corn, potatoes, oil plants, cotton, sugarcane and other crops after seeds are harvested. China is a big agricultural country, and most of crop straws which are produced by 7 hundred million or more tons per year are still incinerated, so that resource waste and environmental pollution are caused. The utilization of crop straws has been internationally regarded as a strategic industry for developing renewable energy resources in the 21 st century, and the resource utilization of crop straws mainly focuses on the development of chemical engineering and building materials. At present, the application research of crop straws as building materials is a hotspot, but the research of directly using crop straws as raw materials of water reducing agents is less. The main components of the straw are cellulose, hemicellulose, lignin and other bio-based macromolecules, the molecules contain ether groups, carbon-carbon double bonds, propenol hydroxyl groups, phenolic hydroxyl groups, carbonyl groups, methoxyl groups, carboxyl groups, benzene rings and other functional groups and chemical bonds, graft copolymerization and cross-linking copolymerization reactions such as etherification, esterification, sulfonation, amidation and the like can be carried out, and the obtained product has special performance.
With the increasing attention on environmental protection, people also care about the safety of the building material and the environment while pursuing the performance of the building material, so that a synthetic method needs to be explored urgently to research and develop a new high-efficiency water reducing agent. The straw bio-based water reducing agent meets the requirements of national policies and markets, but the research on the aspect is still in the laboratory stage and does not enter the engineering application stage. The straw bio-based water reducing agent has good water reducing effect, retarding and slump retaining effects, and the crop straw is rich in resources, low in price, non-toxic and degradable. Has better industrial prospect, but is just in the preliminary stage of research at present and is not widely applied. In recent two years, scholars continuously explore a synthesis method of the straw bio-based water reducing agent by modifying straws.
At present, few research reports of directly using biomass straws as a water reducing agent exist, and most of the research reports are that cellulose and lignin are extracted and separated from the straws, or black liquor wastewater obtained by producing paper making and ethanol from the straws is used as a raw material for modification research of the water reducing agent or compounding research with a polycarboxylic acid water reducing agent.
A study on a lignin modified water reducer, CN 101337789A, a method for preparing the water reducer by condensation modification of wheat straw alkali lignin, includes the steps of adding wheat straw alkali lignin into water with the weight of 4.4-5.5 times of that of wheat straw alkali lignin for dissolution, adding copper sulfate with the weight of 0.6-0.9% of that of the wheat straw alkali lignin, adjusting the pH value to 10-11 by using a caustic soda solution, adding anhydrous sodium sulfite with the weight of 45-55% of that of the wheat straw alkali lignin, heating to 88-92 ℃, reacting for 4-5 hours to obtain a sulfonated product, and carrying out condensation reaction on the sulfonated product and quantitative formaldehyde under the conditions of the pH value of 11.6-12.0 and the temperature of 65-75 ℃ to obtain the water reducer. The water reducing agent prepared by the method has low water reducing rate and can only be used as the most common water reducing agent. Chinese patent CN 101759856B "preparation method of sodium lignosulfonate water reducer", takes black liquor produced by soda boiling of corncobs, corncob acid hydrolysis residues, bagasse or corn stalks as raw materials, and prepares the sodium lignosulfonate water reducer with low water content by coarse filtration, ultrafiltration membrane concentration, sulfonation and spray drying. Chinese patent CN 106698993A, "a polycarboxylate water reducing agent", utilizes waste white mud to size, heat, mix with corn stalk again, add sodium dodecyl sulfate, dry and extrude the piece after stirring, the acid leaching obtains the hydrolyzate, utilize CaO to adjust the straw hydrolyzate to pH value 6.0-7.0, the hydrolyzate that obtains is dried, oxidized, sulfonated, add to polycarboxylate water reducing agent, use ultrasonic treatment 1-2 h after stirring evenly, obtain modified polycarboxylate water reducing agent. The method has the main advantages that the papermaking waste liquid is used for preparing the polycarboxylic acid water reducing agent, waste materials can be well changed into valuable materials, and the strong base in the papermaking waste liquid is utilized to pretreat the corn straws, so that the corn straws can be better soaked in acid for hydrolysis. The essence of the method is that lignin in the straws is sulfonated and compounded with a water reducing agent. Chinese patent CN 102936110A, "a lignosulfonate-polycarboxylic acid copolymerization composite high-performance water reducing agent and a preparation method thereof", is obtained by directly synthesizing lignosulfonate, methyl allyl polyoxyethylene ether and acrylic acid under the action of ammonium persulfate and neutralizing with sodium hydroxide. The essence of the water reducing agent is a lignosulfonate modified polycarboxylic acid water reducing agent.
The research of directly using biomass straws as a water reducing agent mainly has two reports at present: chinese patent CN 106279574A 'A polycarboxylate superplasticizer modified by straws and a preparation method thereof', the first step is straw pretreatment: crushing straws, adding dilute acid, uniformly stirring and mixing, soaking for 18-36 h, filtering, and washing the straws to be neutral by using clear water; step two, preparing the straw modified polycarboxylate superplasticizer: adding methallyl polyoxyethylene-1000, methallyl polyoxyethylene-2400, maleic anhydride, acrylamide, sodium methallyl sulfonate and straws into a four-reflux device and a constant-pressure dropping funnel, adding ammonium persulfate into the constant-pressure dropping funnel, beginning to drop initiator ammonium persulfate at a dropping speed of 2-4 drops/s, and preserving heat for 4-5 hours after dropping; cooling to 35-45 ℃, and adjusting the pH value to 6.8-7.2 to obtain the straw modified polycarboxylic acid water reducing agent. Chinese patent CN 105713164B, "an aliphatic water-reducing agent prepared from straws and a preparation method thereof", is prepared by the steps of straw acid cleaning, straw modified aliphatic water-reducing agent and the like. The method specifically comprises the following steps: pretreating straws, namely crushing corn straws or wheat straws, adding dilute acid, uniformly stirring and mixing, soaking for 18-36 h, filtering, and washing the straws to be neutral by using clear water; adding water into a reaction kettle, then adding sodium sulfite, and dissolving; adding acetone into the dissolved sodium sulfite solution, and sulfonating for 8-12 min; then adding the pretreated straws, and stirring and reacting for 20-40 min; adding formaldehyde into the solution, and reacting at 90-95 ℃ for 1-2 h to prepare the straw modified aliphatic water reducer. The technology effectively utilizes the straw waste resources, overcomes the defect of poor retarding effect of the existing aliphatic water reducing agent, improves the application range of the aliphatic water reducing agent, and reduces the production cost. However, the two research results are only small test shaking tests in laboratories, firstly, the degree and method of fine crushing are not provided for crushing the straws, but only the crushing of the straws, secondly, excessive chloride ions and sulfate ions are brought in by the hydrolysis of the straws by using conventional dilute hydrochloric acid or dilute sulfuric acid to influence the performance of the water reducing agent, thirdly, the conception and concept of industrial tests are not provided, and a great distance is provided from industrialization.
Disclosure of Invention
The invention aims to provide a preparation method of an ester ether sulfonated composite water reducing agent based on straw modification, which comprises the steps of crushing and hydrolyzing crop straw raw materials, carrying out step-by-step sulfonation modification on straw lignin and cellulose to form sulfonate, and carrying out lignocellulose esterification modification to obtain the straw-based ester ether sulfonated composite water reducing agent, so that the problem that the water reducing rate of the straw-based water reducing agent is 10-15% lower is solved.
The technical scheme adopted by the invention is as follows: a preparation method of an ester ether sulfonated composite water reducing agent based on straw modification is characterized in that the water reducing agent is prepared by carrying out primary oxidation-sulfonated esterification modification, secondary oxidation-sulfonated esterification modification and primary hydroxymethylation-etherification modification on crop straw hydrolysis powder in sequence.
The hydrolyzed straw powder is obtained by hydrolyzing straw powder after pretreatment of primary crushing, cleaning, drying, fine crushing and micro crushing of crop straws, and specifically comprises the following two steps:
(1) the invention relates to pretreatment of straw raw material primary crushing, cleaning, drying, fine crushing and micro crushing, which comprises the following specific steps:
the first step is as follows: after a certain amount of raw material straw bundles are naturally air-dried, firstly crushing the raw material straw bundles into straw sections of 1-3 cm;
the second step is that: cleaning the primarily crushed straw sections;
the third step: drying the cleaned straws respectively to enable the water content of the dried straws to be below 10%;
the fourth step: the dried straw sections are further crushed and sieved, and the sieved straw fine crushed materials with the particle size of less than 5mm are obtained;
the fifth step: and performing ball milling and micro-crushing on the straw fine crushed material by using a ball mill, and controlling the discharge granularity below 400 mu m after ball milling to obtain straw powder.
The ball mill is a horizontal ball mill, and the ball milling parameters are as follows: the particle size of the straw raw material is less than 5mm, the rotating speed is 10-50 r/min, the loading amount of the straw raw material is 10-15 Kg, the diameter of copper balls is 10-15 mm, the ball milling time is 10-15 min, and the particle size of discharged materials is 75-400 mu m.
(2) The straw powder hydrolysis process comprises the following specific steps:
the first step is as follows: feeding the straw powder prepared by ball milling pretreatment into a screw extrusion straw hydrolysis machine for hydrolysis;
the second step is that: in the hydrolysis process, firstly, heating the machine body to 50-60 ℃;
the third step: slowly adding No. 1, No. 2 and No. 3 preparation solutions into a screw extrusion straw hydrolysis machine, wherein the No. 1, No. 2 and No. 3 preparation solutions are respectively a lubricating additive, a hydrolysis main catalytic acid and a cocatalyst acid, performing thermal insulation hydrolysis for 10min at a certain screw rotation speed, and then discharging materials into a screw extrusion modification reaction unit for modification reaction;
the lubricating additive is one or a combination of stearic acid and oleic acid;
the solid-to-solid ratio of the straw to the lubricating additive is 1000 g: 6-10 ml; the main hydrolysis catalytic acid solution is one or a combination of more of monocarboxylic acid, dicarboxylic acid or polycarboxylic acid;
the solid acid ratio of the straw to the hydrolysis main catalytic acid is 1000 g: 10-30 ml, the adding amount of the acid is reduced along with H & lt + & gt released by the monobasic acid, the dibasic acid and the polybasic acid, and when the monocarboxylic acid is added, the solid acid ratio of the straw to the hydrolysis main catalytic acid is 1000 g: 30 ml; when dicarboxylic acid is added, straw: the solid acid ratio of the main catalytic acid is 1000 g to 20 ml; when the tricarboxylic acid is added, the solid acid ratio of the straw to the main catalytic acid is 1000 g to 15 ml;
the hydrolysis catalysis-assisting acid preparation solution is dilute sulfuric acid or dilute hydrochloric acid with the mass concentration of 30 g/L, and the solid-acid ratio of the straw to the hydrolysis catalysis-assisting acid is 1000 g: 100 ml.
The screw-extrusion straw hydrolysis machine is a single/double screw extruder, and the rotating speed of a motor is controlled to be 50-80 r/min.
The obtained straw hydrolysis powder is discharged into a spiral extrusion modification reaction unit for modification reaction, and the modification is realized through the following steps:
(1) the primary oxidation-sulfonation esterification modification comprises the following specific steps:
the first step is as follows: feeding the straw material obtained by hydrolysis pretreatment of straw powder into a screw extrusion modification reaction unit formed by connecting No. 1, No. 2, No. 3 and No. 4 screw extruders in series;
the second step is that: in the modification reaction process, firstly, heating the machine body to heat the material to 45-55 ℃;
the third step: the material firstly enters a No. 1 screw extruder, an oxidant is slowly added into the No. 1 screw extruder, and the material is discharged and enters a No. 2 screw extruder after oxidation chain scission reaction for a certain time;
the fourth step: starting a new round of straw materials, feeding the straw materials into a No. 1 screw extruder, and repeating the third step to perform oxidation chain scission reaction;
the fifth step: feeding the No. 1 screw extruder into No. 2 screw extruder, adding acid sulfonating agent into No. 2 screw extruder, sulfonating for certain time, feeding into No. 3 and No. 4 screw extruder, further maintaining temperature, oxidizing and sulfonating for certain time to obtain black straw lignocellulose material, and feeding into straw dissolving tank;
and a sixth step: adding water into a straw dissolving tank, stirring, dissolving, and then allowing the straw dissolving tank to enter a reaction kettle for secondary sulfonation esterification and primary hydroxymethylation-etherification modification treatment of straw lignocellulose;
(2) the secondary oxidation-sulfonation esterification modification and the primary hydroxymethylation-etherification modification comprise the following specific processes:
the first step is as follows: firstly, deionized water with the temperature of 45-55 ℃ is added into a reaction kettle, and the materials are uniformly mixed by stirring at a low speed to prepare a base solution with a certain concentration;
the second step is that: then heating the body of the reaction kettle to heat the material to 55-60 ℃;
the third step: firstly adding an oxidant, stirring for oxidation reaction for a certain time, adding an alkali liquor, stirring and adjusting the pH value to 7.5-8.0, then adding a weakly alkaline sulfonating agent, stirring for sulfonation reaction for a certain time, adding a hydroxymethylation reagent, stirring for hydroxymethylation reaction for a certain time, finally adding an etherifying agent, preserving heat, stirring for reaction for a certain time, and naturally cooling to normal temperature to obtain the straw lignocellulose ester ether sulfonated viscous liquid water reducing agent with a certain concentration and light brown color, namely the obtained product.
The invention also includes storage and anti-settling cycles for the product as follows:
the first step is as follows: pumping the water reducer product prepared in the reaction kettle group into an annular liquid inlet main pipe right above a finished product storage tank group, and discharging the water reducer product into each storage tank through liquid inlet branch pipes which are distributed on the annular liquid inlet main pipe and correspondingly connected with each storage tank, wherein the storage tanks are distributed in an annular matrix;
the second step is that: when the finished product storage tank is placed for a period of time and precipitates appear at the lower end of the finished product storage tank, a circulating liquid discharge pump arranged on the periphery of the lower end of the finished product storage tank set is started, the precipitated liquid at the lower part of each storage tank is pumped into an annular liquid discharge main pipe, the annular liquid discharge main pipe is communicated with the annular liquid inlet main pipe, liquid is discharged into a corresponding storage tank through liquid inlet branch pipes, liquid and top continuous circulating liquid inlet are performed from the bottom of the storage tank set, after the circulation is performed for a period of time, the water reducing agent liquid in the storage tank set is uniformly mixed, the precipitate is dissolved and disappears, and the circulation is stopped.
The ester ether sulfonated composite water reducing agent based on straw modification prepared by the method disclosed by the invention is applied to cement paste and concrete.
The ester ether sulfonated composite water reducing agent prepared by the method has initial cement paste fluidity of 240mm, 60min fluidity of 210mm and 120min fluidity of 180mm under the condition that the mixing amount of the cement paste is 0.30%.
The invention has the following advantages:
1. according to the invention, the crop straw raw material is subjected to crushing and hydrolysis pretreatment, the straw lignin and cellulose are subjected to step-by-step sulfonation modification to form sulfonate, and then the lignocellulose is subjected to cellulose esterification modification to obtain the straw-based ester ether sulfonated composite water reducing agent, so that the problem that the water reducing rate of the straw-based water reducing agent is relatively low by 10-15% is solved, and the obtained water reducing agent can be directly used under the conditions that the water reducing rate is about 25% and the retardation time is moderate. The invention has the advantages of continuous and compact process, simple equipment, easy operation, high straw micro-crushing and hydrolyzing efficiency, good straw modification effect, low cost, precipitation prevention and easy industrialization.
2. According to the invention, the cleaned straw sections are subjected to the drying process of the pre-drying device and the spiral dryer, the hot air used by the pre-drying device is the waste heat air exhausted by the spiral dryer, the full utilization of energy is realized, the drying efficiency is high, and the water content of the straw is easily calculated by mass percent at the level of below 10%;
3. the invention utilizes the characteristics of the ball mill, the straw sections with the diameter less than 5mm are easily micro-crushed into straw powder with the diameter of 75-400 mu m, lignin in the straw is basically destroyed after the treatment, and the cellulose is easier to hydrolyze due to the degradation of the lignin. The crystallinity of the straw is reduced after long-time ball milling, and the ratio of amorphous cellulose and the reaction active area are increased, so that the cellulose of the straw is easier to permeate and hydrolyze by weak acid.
4. The biomass macromolecule components such as cellulose, hemicellulose, lignin and the like of the crop straws are fully utilized, the macromolecules contain various functional groups such as ether groups, carbon-carbon double bonds, propenol hydroxyl groups, phenolic hydroxyl groups, carbonyl groups, methoxyl groups, carboxyl groups, benzene rings and the like and the complex characteristics of chemical bonds, the water content of the straws is about 10 percent by adopting a semi-dry method, and the straws are degraded by adding a liquid-phase hydrolysis catalytic acid spiral extrusion combined organic/inorganic acid mixed acid pretreatment method, so that the straw raw material has the advantages of small corrosion to equipment, high degradation rate, simple reaction process, mild reaction conditions, low cost and easy industrial application; and the adverse effects of excessive chloride ions or sulfate ions on the corrosion of the subsequent water reducing agent on concrete and the like caused by only using inorganic acid, hydrochloric acid or sulfuric acid to degrade the straws are avoided or reduced.
5. The organic acid main catalyst used in the semi-dry spiral extrusion combined organic/inorganic acid mixed acid pretreatment of the straw raw material can be used as an unsaturated small molecular monomer required by a water reducing agent, particularly an unsaturated carboxylic acid small molecular monomer, and the performance of the product is not influenced by slight addition of excessive amount; during the pretreatment of the straw lignocellulose raw material by combining the semidry method screw extrusion with the organic/inorganic acid mixed acid, not only are the straw lignin, hemicellulose and cellulose further separated, but also the main products of straw hydrolysis are mannose, glucose, galactose, xylose and arabinose. Meanwhile, various complex reactions occur, some small molecular compounds are generated along with the reactions, the generated small molecular compounds can be used as small molecular monomers required for synthesizing the water reducing agent, and have respective characteristics, such as the retarding and water reducing effects of monosaccharide, polysaccharide and carboxylic acid, the slump retaining effect of furfural and phenolic compounds and the like, and the generated organic weak acids such as formic acid, acetic acid, levulinic acid and the like provide H +, so that the hydrolysis is promoted, the hydrolysis process is accelerated, the degradation of cellulose and lignin in the straw is remarkably promoted, the saccharification rate is high, the reaction conditions are mild, the reaction process is simple and basically pollution-free, and the industrial production is easy.
6. The invention further reduces the crystallinity of the straws and further increases the ratio of amorphous cellulose and the reaction active area by utilizing the characteristics of the screw extruder in functions of horizontal flow, high-speed extrusion and strong shearing and the functions of long-time high-speed extrusion and strong shearing, so that the cellulose of the straws is easier to permeate and hydrolyze by weak acid, and the hydrolysis of the straws is more efficient and easy to control. Meanwhile, the shell of the screw extrusion machine body is provided with the coil type heat exchanger, so that the temperature is convenient to rise, the reaction is accelerated, and the operation is easy;
7. the sulfonation modification process of the straw lignocellulose adopts step-by-step sulfonation, firstly, a semi-dry method is adopted in a screw extrusion sulfonation modification reaction unit for preliminary oxidation-sulfonation modification, and sulfonating agents suitable for an acidic system, such as chlorosulfonic acid, sulfamic acid and sodium bisulfite, are adopted as sulfonating agents to react with straw hydrolyzed powder in a semi-dry method solid-liquid phase manner, so that the sulfonation of the cellulose in the straw is mainly carried out, while lignin hardly participates in the sulfonation in a weakly acidic environment, as the sulfonation is carried out, the acidity of hydroxyl in a molecular chain of the straw cellulose is weakened, the activity is reduced, the sulfonation rate of the straw cellulose is reduced, the substitution degree of sulfonic acid groups is lower, the water solubility of a product is not good, the water reducing performance is poorer, and meanwhile, the pH value of the material is gradually increased; and then, further oxidizing-sulfonating the primary sulfonated modified substance in a reaction kettle by adopting a liquid phase method, reacting sodium sulfite Na2SO3 suitable for a weak alkaline system in an aqueous solution, adding liquid alkali to adjust the pH value to be 7.5-8.0 in a weak alkaline environment, improving the activity of phenolic hydroxyl which does not participate in lignin in the early stage, accelerating the sulfonation rate of the lignin, finally improving the sulfonation efficiency of the straw lignocellulose, further increasing the substitution degree of sulfonic acid groups and increasing the water solubility of a product. Meanwhile, in an alkaline environment, the alkali cellulose and lignin are easy to be subjected to hydroxymethylation, more active hydroxyl groups are provided, and the hydroxyl groups react with an etherifying agent monochloroacetic acid to obtain lignocellulose substituent ether, so that the solubility of the modified material in water is increased, and the modified material has better water-reducing dispersion performance.
8. The screw extrusion hydrolysis machine/screw extrusion sulfonation modification reaction unit is matched with the batching storage tank group, so that respective liquid preparation control and step-by-step feeding are facilitated, the screw extrusion sulfonation modification reaction units are connected in series, the step-by-step control feeding of a modification reagent is facilitated, and the intermittent continuous propulsion operation process is easy to realize. The liquid level meter and the liquid level graduated scale are arranged in each batching storage tank group, so that the liquid material feeding amount can be monitored preliminarily, and the liquid discharge pipeline is provided with the precise flow meter, so that the liquid material feeding amount can be controlled precisely. The invention adopts the suspension type measuring bin weighing device, can accurately weigh straw powder and straw wet materials, is convenient for accurately putting the powder and ensures the product quality. The invention adopts the reaction kettle group 33 and the finished product storage tank group 34 which are in an annular matrix distributed structure, thereby being convenient for operation and control and having high production efficiency. The finished product storage tank group 34 in an annular matrix distributed structure is adopted to prevent a sedimentation circulating system, so that the uniformity of product components and the stability of quality are ensured.
Drawings
FIG. 1 is a flow diagram of a process apparatus of the present invention;
in the figure, 1-equipment rack; 2-a straw primary crushing device; 3-bundling the raw material straws; 4-1 # straw primary crushed material lifting conveying air duct; 5-a cleaning device; 6-a pre-drying device; 7-lifting the wet straw material on a conveying belt; 8-a spiral dryer; 9-a cyclone separator; 10-1 # aggregate bin; 11-2 # aggregate bin; 12-2 # straw primary crushed material lifting conveying air duct; 13-3 # aggregate bin; 14-a rotary screening device; 15-a straw fine crushing device; 16-material sealing and collecting cover; 17-1 # measuring bin weighing device; 18-horizontal ball mill micro-crushing device; 19-lifting the straw powder to a conveying air duct; 20-4 # aggregate bin; 21-2 # measuring bin weighing device; 22-a screw-extrusion straw hydrolysis machine; 23-1 # liquid phase ingredient storage tank group; 24-1 # heater; 25-2 # liquid phase ingredient storage tank group; 26-a screw extrusion modification reaction unit; 27-3 # liquid phase ingredient storage tank group; 28-2 # heater; no. 29-3 measuring bin weighing device; 30-a straw dissolving tank; 31-a water tank; 32-3 # heater; 33-a reaction kettle group; 34-finished product storage tank group;
FIG. 2 is an assembly view of the equipment accessories of the present invention, not otherwise shown in the production system diagram;
in the figure, 1-equipment rack; 2-a straw primary crushing device; 3-bundling the raw material straws; 4-1 # straw primary crushed material lifting conveying air duct; 5-a cleaning device; 6-a pre-drying device; 7-lifting the wet straw material on a conveying belt; 8-a spiral dryer; 801-drying chamber; 802-screw feeder; 803-hot air outlet; 804-an electric stirring device; 805-hot air distributor; 806-an electric heater; 807-a blower; 9-a cyclone separator; 901-cyclone feed inlet; 902-a bleed port at the upper end of the cyclone; 903-a line filter; 904-star discharger; 905-a discharge pipe; 906-an inlet pipe of a draught fan; 907-induced draft fan; 908-residual heat delivery pipe at the outlet of the induced draft fan; 10-1 # aggregate bin; 101-star discharger; 102-a discharge pipe; 11-2 # aggregate bin; 111-star discharger; 112-a discharge pipe; 113-axial flow fan; 12-2 # straw primary crushed material lifting conveying air duct; 13-3 # aggregate bin; 14-a rotary screening device; 15-a straw fine crushing device; 16-material sealing and collecting cover; 17-1 # measuring bin weighing device; 18-horizontal ball mill micro-crushing device; 181-screw feeder; 182-a transmission motor; 183-discharge port; 19-lifting the straw powder to a conveying air duct; 20-4 # aggregate bin; 21-2 # measuring bin weighing device; 22-a screw-extrusion straw hydrolysis machine; 23-1 # liquid phase ingredient storage tank group; 24-1 # heater; 25-2 # liquid phase ingredient storage tank group; 26-a screw extrusion modification reaction unit; 27-3 # liquid phase ingredient storage tank group; 28-2 # heater; no. 29-3 measuring bin weighing device; 30-a dissolving tank; 31-a water tank; 32-3 # heater; 33-a reaction kettle group; 34-finished product storage tank group;
FIG. 3 is a front sectional view of the straw crushing apparatus of the present invention;
in the figure, 1-equipment rack; 201-a blower; 202-W type stainless steel screen; 203-star type driving knife roll; 204-inclined baffles; 205-a rack; 206-driving carrier roller group conveyer belt; 207-active carrier roller group; 208-V type feed inlet; 209-V type feed inlet cover plate; 210-a driven carrier roller set; 211-upper cavity of the straw primary crushing chamber; 212-dust discharge duct; 213-star-shaped driven knife roll; 214-middle cavity of the straw primary crushing chamber; 215-lower cavity of the straw primary crushing chamber; 216-axial fan; 217-discharge port; 218-sloping plate stainless steel screen; 219-dust collecting chamber; 220-dust collecting tank; 3-bundling the raw material straws; 4-1 # straw primary crushed material lifting conveying air duct;
FIG. 4 is a sectional view A-A of the straw crushing apparatus of the present invention;
in the figure, 1-equipment rack; 202-W type stainless steel screen; 203-star type driving knife roll; 204-inclined baffles; 205-a rack; 206-driving carrier roller group conveyer belt; 207-active carrier roller group; 208-V type feed inlet; 211-upper cavity of the straw primary crushing chamber; 214-middle cavity of the straw primary crushing chamber; 215-lower cavity of the straw primary crushing chamber; 218-sloping plate stainless steel screen; 219-dust collecting chamber; 220-dust collecting tank; 221-star-shaped driving knife roller transmission motor; 222-driving carrier roller group driving motor; 223-driving carrier roller group driving belt; 3-bundling the raw material straws;
FIG. 5 is a schematic view of the position assembly of the cleaning device and the pre-drying device of the present invention;
in the figure, 1-equipment rack; 4-1 # straw primary crushed material lifting conveying air duct; 51-a straw cleaning tank; 5101-a liquid discharge port; 5102-a lower filter screen; 5103-manhole; 5104-stirring blade; 5105-stirring shaft; 5106-stirring motor; 5107-filtering net at upper end; 5108-circulating water supply pipe; 5109 circulation water supply pipe water inlet; 5110-raw water inlet; 5111-feeding inlet of straw coarse material; 5112-baffle; 52-filtered water collecting tank; 5201-a manhole; 5202-a filter screen; 5203-a centrifugal pump; 5204-drain pipe; 5205-a pump water outlet pipe controls a three-way valve; 5206-a sewage draining pipe; 6-a pre-drying device;
FIG. 6 is an enlarged view of a portion A of FIG. 5;
in the figure: 51-a straw cleaning tank; 5113-straw discharge pipe; 601-a spring tube; 602-a spring support plate; 611-a straw feed inlet; 603-stainless steel punching filter screen plate; 604-driven idler support frame; 605-driven roller for straw dehydration; 606-straw dewatering driving carrier roller; 607-motor drive belt; 608-a drive motor; 609-a motor support frame; 610-driving carrier roller supporting frame; 611-a straw feed inlet; 613-dust filter screen; 631-a pre-drying chamber;
FIG. 7 is a front sectional view of the pre-drying apparatus of the present invention;
in the figure: 5113-straw discharge pipe; 601-a spring tube; 602-a spring support plate; 611-a straw feed inlet; 603-stainless steel punching filter screen plate; 604-driven idler support frame; 605-driven roller for straw dehydration; 606-straw dewatering driving carrier roller; 607-motor drive belt; 608-a drive motor; 609-a motor support frame; 610-driving carrier roller supporting frame; 611-a straw feed inlet; 612-evacuation chimney; 613-dust filter screen; 614-1 # heat-resistant conveyer belt; 615-2 # heat-resistant conveyer belt; 616-3 # heat-resistant conveyer belt; 617-4 # heat-resistant conveyer belt; 618 # 5 heat-resistant conveyer belt; 619-6 # heat-resistant conveyer belt; 620-7 # heat-resistant conveyer belt; 621. 622-motor drive belt; 623-a stainless steel perforated mesh receiving disc; 624-hot air distributor; 625-an axial fan; 626-discharge port; 631-a pre-drying chamber;
FIG. 8 is a left side view of the pre-drying apparatus of the present invention;
in the figure: 1-equipment support; 606-straw dewatering driving carrier roller; 607-motor drive belt; 608-a drive motor; 609-a motor support frame; 610-driving carrier roller supporting frame; 611-a straw feed inlet; 612-evacuation chimney; 613-dust filter screen; 614-1 # heat-resistant conveyer belt; 615-2 # heat-resistant conveyer belt; 618 # 5 heat-resistant conveyer belt; 619-6 # heat-resistant conveyer belt; 620-7 # heat-resistant conveyer belt; 621. 622-motor drive belt; 623-a stainless steel perforated mesh receiving disc; 624-hot air distributor; 625-an axial fan; 626-discharge port; 627. 628-a drive motor;
FIG. 9 is a sectional view taken along line A-A of the predrying apparatus of the present invention;
in the figure: 614-1 # heat-resistant conveyer belt; 6141-1 # heat-resisting conveyer belt driving carrier roller; 6142-1 # heat-resisting conveyer belt driven idler; 6143-small round hole; 615-2 # heat-resistant conveyer belt; 6151-2 # heat-resisting conveyer belt driving carrier roller; 6152-2 # heat-resisting conveyer belt driven idler; 621. 622-motor drive belt; 627. 628-a drive motor; 629-1 # Heat-resistant conveyer belt gear transmission belt; 630-2 # heat-resisting conveyer belt gear transmission belt; 631-a pre-drying chamber;
FIG. 10 is a schematic view of a hot air distributor of the pre-drying apparatus according to the present invention;
in the figure: 6241-vertical hot air intake manifold; 6242-transverse secondary air-distributing pipe; 6243-longitudinal tertiary air-distributing pipe; 6244-gas-distributing small round holes; 625-an axial fan;
FIG. 11 is a schematic view of the assembly positions of the rotary screening device, the straw crushing device, the material sealing and collecting cover and the No. 1 metering bin weighing device of the invention;
in the figure: 1-equipment support; 12-2 # straw primary crushed material lifting conveying air duct; 13-3 # aggregate bin; 14-a rotary screening device; 15-a straw fine crushing device; 16-material sealing and collecting cover; 1601-star discharger; 1602-connecting a hose; 1701-hanger fixing plate; 1702-platform scale support platform fixed hanger; 1703-feed inlet; 1704-pound scale; 1705-platform scale support platform; 1706-star discharger; 1707-a metering bin;
FIG. 12 is a schematic view of the assembly position between the rotary screening device and the straw crushing device of the present invention;
in the figure: 1-equipment support; 141-a first transmission motor; 142A, 142B-bearings; 143A-bearing support; 143B-bearing housing; 144-a first shaft; 145-rotary sifting chamber; 1451-rotary sifting chamber feeding baffle; 1452-a rotating shaft star-shaped bracket; 1453 & 143B bearing sleeve star-shaped bracket; 1454-rack; 1455-rotating the sieving chamber cavity housing; 1456-stainless steel screen mesh; 1457-flanging; 151-second transmission motor; 152-a bearing; 153-a bearing seat; 154-a coupling; 155-a bearing; 156-a bearing seat; 157-shaft sleeve; 158-rotating sifting chamber tailgate; 159-straw fine crushing cutter group; 1591-initial positioning baffle of fine crushing cutter group; 1592-fine crushing cutter; 1593-backing plate between knives; 1594-second axis of rotation; 1595-positioning baffle at the tail end of the fine crushing cutter group; 1596-fastening nut;
FIG. 13 is a sectional view taken along line A-A of FIG. 12;
in the figure: 1454-rack; 1455-rotating the sieving chamber cavity housing; 1456-stainless steel screen mesh; 1457-flanging; 14571-screw hole; 15921-shear blade; 15922-shear blade circumferential distribution fixing plate; 1594-second axis of rotation; 15941-axle key;
FIG. 14 is a schematic illustration of the skeletal structure of a rotary screening device of the present invention;
in the figure: 1-equipment support; 141-a first transmission motor; 142A-bearing; 143A-142A bearing support; 143B-142B bearing supports; 144-a first shaft; 1451-rotary sifting chamber feeding baffle; 1452-a rotating shaft star-shaped bracket; 1453-53B bearing sleeve star-shaped bracket; 1454-rack; 1455-rotating the sieving chamber cavity housing; 1457-flanging; 14571-screw hole; 1458-axially fixing reinforcing ribs on a screen of the rotary screening chamber; 1459-fixing reinforcing ribs on the circumferential direction of the screen of the rotary screening chamber;
FIG. 15 is an isometric view of a rotary screening device of the present invention;
in the figure: 1-equipment support; 141-a first transmission motor; 142A-bearing; 143A-142A bearing support; 144-a first shaft; 1451-rotary sifting chamber feeding baffle; 1456A-stainless steel diamond or square mesh; 1456B stainless steel perforated small round hole screen; 1457-flanging; 14571-screw hole; 1458-axially fixing reinforcing ribs on a screen of the rotary screening chamber; 1459-fixing reinforcing ribs on the circumferential direction of the rotary screening chamber screen circular screen;
FIG. 16 is a front sectional view of the straw crushing apparatus of the present invention;
in the figure: 1-equipment support; 151-second transmission motor; 152-a bearing; 153-a bearing seat; 154-a coupling; 155-a bearing; 156-a bearing seat; 157-shaft sleeve; 158-rotating sifting chamber tailgate; 159-straw fine crushing cutter group; 1591-initial positioning baffle of fine crushing cutter group; 1592-fine crushing cutter; 1593-backing plate between knives; 1594-second axis of rotation; 1595-positioning baffle at the tail end of the fine crushing cutter group; 1596-fastening nut;
FIG. 17 is a sectional view taken along line A-A of the straw crushing apparatus of the present invention;
in the figure: 158-rotating sifting chamber tailgate; 1581-screw hole; 15921-shear blade; 15922-shear blade circumferential distribution fixing plate; 1593-backing plate between knives; 1594-second axis of rotation; 15941-axle key;
FIG. 18 is a schematic structural diagram of a fine crushing cutter set of the straw fine crushing device of the present invention;
in the figure: 15921-shear blade; 15922-shear blade circumferential distribution fixing plate; 15923-shaft through hole; 15924-keyway;
FIG. 19 is a sectional view A-A of FIG. 18;
in the figure: 15921-shear blade; 15922-shear blade circumferential distribution fixing plate; 15923-shaft through hole;
fig. 20 is a schematic view of the assembly position between the 4 # aggregate bin and the weighing device of the metering bin of the invention:
in the figure: no. 201-4 aggregate bin feed inlet; 202-an aggregate bin; 203-star discharger; 204-connecting hose; 211-a dosing bin; 212-hanger plate support bracket; 213-platform scale/platform scale supporting platform fixing hanger; 214-hanger fixation plate; 215-metering bin feed inlet; 216-platform scale/platform scale; 217-scale/platform scale support platform; 218-star discharger; 219-connecting hose;
FIG. 21 is a schematic diagram of the assembly position between the screw extrusion hydrolysis machine of the present invention and the No. 1 liquid-phase ingredient storage tank set and the No. 1 heater:
in the figure: 221-screw extruder feed inlet; 222-a screw extruder; 223-driving motor and reducer; 224-screw; 225-coil heater; 226-star discharger; no. 231-1 ingredient storage tank; 2311-a communicating level gauge; 2312-level gauge scale; 2313-agitator; 2314-drive motor; 2315-a discharge valve; 232-2 # ingredient storage tank; 233-3 # ingredient storage tank; no. 234-4 ingredient storage tank; 235-a discharge main; 2351-discharge main pipe tapping valve; 2401-heating the water tank; 2402-a thermometer; 2403-raw water inlet; 2404-manhole; 2405-a water return port; 2406-coiled tube heat exchanger return water control valve; 2407-a coil heat exchanger water inlet control valve; 2408-hot water pump; 2409-heating water tank water outlet control valve; 2410-a sewage draining outlet; 2411-electric heating wire;
FIG. 22 is a schematic diagram of the assembly positions of the screw extrusion modification reaction unit, the No. 2 liquid-phase ingredient storage tank unit and the No. 2 heater of the present invention:
in the figure: no. 251-1 ingredient storage tank; 2511-a communication type level gauge; 2512-level gauge scale; 2513-a stirrer; 2514-discharge three-way valve; 2515-drive motor; no. 252-2 ingredient storage tank; no. 253-3 ingredient storage tank; 254-4 # ingredient storage tank; 255-a discharge header; 255-1-a discharge main liquid discharge valve; 256-4 # batching storage tank discharge pipe; 257-3 # batching storage tank discharging tube; 258-2 # batching storage tank discharging pipe; 259-1 # batching storage tank discharge pipe; no. 261-1 screw extruder; 2611-screw extruder feed port; 2612-screw extruder discharge control valve; 2613-coil heater return pipe; 2614-screw; 2615-coil heater; 262-2 # screw extruder; no. 263-3 screw extruder; 264-4 # screw extruder; 265-motor drive belt; 266-star discharger; 267-a drive motor; 268-a drive motor; 269-motor drive belt; 2801-heating water tank; 2802-thermometer; 2803-raw water inlet; 2804-manhole; 2805-water return port; 2806-coiled tubing heat exchanger return water control valve; 2807-coil heat exchanger water intake control valve; 2808-hot water pump; 2809-heating tank water outlet control valve; 2810-a sewage draining outlet; 2811-electric heating wire;
fig. 23 is a schematic structural diagram of a 3 # liquid-phase ingredient storage tank set of the invention:
in the figure: 271-1 # ingredient storage tank; 2711-level gauge scale; 2712-communicating type level gauge; 2713-discharge control valve; 272-2 # ingredient storage tank; 273-3 # ingredient storage tank; 2731-stirring motor; 2732-drain control valve; 2733-stirrer; 2734-level gauge scale; 2735-connected level gauge; 2736-drain control valve; 274-4 # ingredient storage tank; 275-5 # ingredient storage tank; 276-6 # ingredient storage tank; 277-1 # drainage main pipe; 2771-1 # drainage main pipe control valve; 278-2 # drainage main; 2781-precision flow meter; 2782-2 # drainage main pipe control valve;
FIG. 24 is a front view of the assembly positions of the reaction kettle set, the straw dissolving tank, the No. 3 heater and the finished product storage tank set;
in the figure: 30-a straw dissolving tank; 301-a discharge pipe valve; 3201-heating the water tank; 3202-a sewage draining outlet; 3203-electric heater; 3204-thermometer; 3205 raw water inlet; 3206-manhole; 3207-heating water tank backwater inlet; 3208-heating water tank return pipe valve; 3209-an annular water return main pipe; 3210-annular main water inlet pipe; 3211-hot water pump outlet pipe valve; 3212-a hot water pump; 3213-heating water tank water outlet control valve; 3214-heating water tank outlet pipe; 3301-connecting tube valve; 3302-annular inlet manifold of reaction kettle group; 3303-5 # reaction kettle; 33031-feeding port of straw solution in reactor; 33032-stirring motor; 33033-feeding liquid into reactor; 33034-inlet of reaction kettle liquid phase material; 33035-stirrer; 3304-discharge pipe valve of liquid discharge pump; 3305-1 # reaction kettle; 33051-liquid discharge tube valve of reaction kettle group; 33052-coiled pipe water inlet pipe valve; 33053-coiled pipe type heating pipe return water pipe valve; 33054-coiled heating tube; 3306-annular main liquid discharge pipe of reaction kettle group; 3307-liquid discharge pump of reaction kettle group; 3308-liquid discharge pump liquid inlet pipe valve; 3314-7 # reaction kettle; 3401-control valve of a liquid inlet main pipe of the finished product storage tank group; 3402-feeding the circulating liquid of the finished product storage tank group into a liquid branch pipe; 3403-feeding liquid into the finished product storage tank group; 3404-high-level communicating pipe valve of the finished product storage tank group; 3405-ring-shaped liquid inlet main pipe of the finished product storage tank group; 3406-controlling pipe valve of circulating liquid inlet main pipe of finished product storage tank group; 3407-discharge pipe valve of finished product storage tank group; 3408-discharge pipe valve of circulation drain pump; 3409-ring-shaped liquid discharge main pipe of the finished product storage tank group; 3410-circulation positive displacement pump; 3411-3 # finished product storage tank; 3412-a finished product storage tank group low-level communicating pipe valve; 3413-1 # finished product storage tank; 34131-a liquid inlet of a circulating liquid of the finished product storage tank group; 34132-finished product tank set liquid inlet; 34133-level gauge scale; 34134-communication type level gauge; 34135-a finished product storage tank discharge port; 34136-product storage tank discharge gate pipe valve; 3416-a liquid inlet control pipe valve of a circulating liquid discharge pump;
FIG. 25 is a plan view of FIG. 24;
in the figure: 30-a straw dissolving tank; 301-a discharge pipe valve; 3201-heating the water tank; 3204-thermometer; 3205 raw water inlet; 3206-manhole; 3207-heating water tank backwater inlet; 3208-heating water tank return pipe valve; 3209-an annular water return main pipe; 3210-annular main water inlet pipe; 3211-hot water pump outlet pipe valve; 3212-a hot water pump; 3213-heating water tank water outlet control valve; 3214-heating water tank outlet pipe; 3301-connecting tube valve; 3302-annular inlet manifold of reaction kettle group; 3303-5 # reaction kettle; 33031-feeding port of solid material in reactor; 33032-stirring motor; 33033-feeding liquid into reactor; 33034-inlet of reaction kettle liquid phase material; 3304-discharge pipe valve of liquid discharge pump; 3305-1 # reaction kettle; 33051-liquid discharge tube valve of reaction kettle group; 33052-coiled pipe water inlet pipe valve; 33053-coiled pipe type heating pipe return water pipe valve; 33054-coiled heating tube; 3306-annular main liquid discharge pipe of reaction kettle group; 3307-liquid discharge pump of reaction kettle group; 3308-liquid discharge pump liquid inlet pipe valve; 3309-high-level connection pipe valve of reaction kettle group; 3310-2 # reaction kettle; 3311-3 # reaction kettle; 3312-4 # reaction kettle; 3313-6 # reaction kettle; 3314-7 # reaction kettle; 3315-8 # reaction kettle; 3401-control valve of a liquid inlet main pipe of the finished product storage tank group; 3402-feeding the circulating liquid of the finished product storage tank group into a liquid branch pipe; 3403-feeding liquid into the finished product storage tank group; 3404-high-level communicating pipe valve of the finished product storage tank group; 3405-ring-shaped liquid inlet main pipe of the finished product storage tank group; 3406-controlling pipe valve of circulating liquid inlet main pipe of finished product storage tank group; 3407-finished product storage tank group outlet pipe valve; 3409-ring-shaped liquid discharge main pipe of the finished product storage tank group; 3410-circulation positive displacement pump; 3411-3 # finished product storage tank; 3413-1 # finished product storage tank; 34131-a liquid inlet of a circulating liquid of the finished product storage tank group; 34132-finished product tank set liquid inlet; 34135-a finished product storage tank discharge port; 34136-product storage tank discharge gate pipe valve; 3414-2 # finished product storage tank; 3415-4 # finished product storage tank; 3416-liquid inlet control pipe valve of circulation liquid discharge pump.
Detailed Description
The method of the present invention is further described in detail below with reference to a process flow diagram;
s1: pretreatment of straw raw materials: the specific operation process is as follows:
the first step is as follows: pre-crushing, cleaning, drying, fine crushing and micro-crushing the straw raw material:
(1) primary crushing of the straws: after a certain amount of wheat/corn/rice/cotton/oil stalk bundles 3 to be treated are naturally air-dried, manually unpacked and arranged on a platform which is flush with a V-shaped feed inlet 208 at the upper end of a stalk primary crushing device 2, manually pushed to enter an upper cavity 211 of a stalk primary crushing chamber and clamped in a pair of V-shaped carrier roller group conveyer belts 206 with concave-convex surfaces, wherein the pair of V-shaped carrier roller group conveyer belts are arranged at the left side and the right side of the upper cavity and driven by a pair of carrier rollers, a main carrier roller group 207 is driven by a transmission motor 222 to rotate, the stalk bundles are subjected to downward friction on the V-shaped carrier roller group conveyer belts 206, the surface layers of the stalk bundles are firstly peeled off and enter a star-shaped knife roller group consisting of a star-shaped driving knife roller 203 and a star-shaped driven knife roller 213 at the right lower end to be sheared and crushed, the star-shaped driving knife roller 203 is driven by the transmission motor 221 to rotate, and part of the incompletely sheared and crushed stalk material is fed into the lower end of the star-shaped knife roller group, the secondary is stirred by the roller teeth and is brought up by force, the secondary and the rack 205 horizontally arranged at the upper end of the middle cavity 214 of the primary straw crushing chamber are sheared and crushed again, the crushed materials fall into the W-shaped stainless steel screen 202 fixed in the middle cavity 214 of the primary straw crushing chamber at the lower end of the star-shaped cutter roller group, the crushed materials after being screened fall into the inclined baffle 204 arranged at the left side and the inclined stainless steel screen 218 arranged at the right side in the lower cavity 215 of the primary straw crushing chamber (the inclined baffle 204 at the left side is connected with the inclined stainless steel screen 218 at the right side), and under the action of the blower 201 arranged at the left side outside the lower cavity 215 of the primary straw crushing chamber and the axial flow fan 216 in the pipeline at the discharge port 217, the crushed straw materials pass through the inclined stainless steel screen 218 and enter the primary straw crushing material lifting and conveying air duct 4 No. 1 to be lifted and conveyed to the cleaning device 5. Meanwhile, sandy soil impurities in the crushed straw fall into the dust collection cavity 219 and further fall into the dust collection tank 220 to be collected and returned to the field. And finishing the primary crushing and conveying process of the straws, wherein the particle size of the crushed straws is 1-3 cm.
(2) Straw cleaning and preliminary dehydration: the primary crushed straw section from the No. 1 primary crushed straw lifting conveying air duct 4 enters a straw cleaning groove 51 containing clear water at the left side of the cleaning device 5 from a coarse straw material feeding hole 5111, a stirring blade 5104 in the vertical direction is driven by a stirring motor 5106, the straws migrate downwards under the stirring action of the stirring blade 5104 and a vertical baffle 5112, under the condition that the lower end of the blade is not stressed, the straws migrate upwards along the groove wall of the straw cleaning groove 51, enter a cleaned straw discharging pipe 5113 at the upper right end and are sent to a space between straw section dewatering carrier rollers consisting of a straw dewatering driven carrier roller 605 and a straw dewatering driving carrier roller 606 at the upper left end of the outer wall of the pre-drying device 6, the driving carrier roller 606 of the dewatering carrier rollers rotates under the action of a transmission motor 608, and the wet straw section falls on a stainless steel punching filter screen plate 603 obliquely arranged at the lower end after being dragged and extruded to primarily dewater between the spaces of the dewatering carrier rollers, the straw falls into the pre-drying device 6 through the straw feeding hole 611 of the pre-drying device 6 to perform the pre-drying process. Meanwhile, the water squeezed out of the straws by the dewatering carrier roller set falls into the filtered water collecting tank 52 of the cleaning device 5 right below through the stainless steel punching filter screen plate 603, and falls into the lower part of the filtered water collecting tank 52 after being filtered by the filter screen 5202, and then falls into the circulating water inlet 5109 of the straw cleaning tank 51 through the circulating water inlet pipe 5108 and the pump water outlet pipe control three-way valve 5205 under the action of the centrifugal pump 5203 through the liquid discharge pipe 5204 at the right lower end, and then enters the straw cleaning tank 51 for recycling again until the straws are seriously polluted and cannot be discharged to return to the field in time, and new water is replaced.
(3) Pre-drying the straw sections: as shown in fig. 5-8, the initial crushed material of the straws after the initial dehydration by the dehydration roller support set falls into the pre-drying chamber 631 through the straw feeding port 611 of the pre-drying device 6, firstly falls on the No. 1 heat-resistant conveyer belt 614, and then falls on the No. 2 heat-resistant conveyer belt 615, the No. 3 heat-resistant conveyer belt 616, the No. 4 heat-resistant conveyer belt 617, the No. 5 heat-resistant conveyer belt 618, the No. 6 heat-resistant conveyer belt 619 and the No. 7 heat-resistant conveyer belt 620 which are folded in a zigzag manner and move in reverse and alternate directions along with the movement of the conveyer belt, and then falls on the discharging port 626 and is discharged. In the process, the heat-resistant conveyer belts are divided into two groups according to the moving trend, wherein the No. 1, No. 3, No. 5 and No. 7 heat-resistant conveyer belts are the group A, the No. 2, No. 4 and No. 6 heat-resistant conveyer belts are the group B, the group A is driven by a transmission motor 627 through a transmission belt 621, the group B is driven by a transmission motor 628 through a transmission belt 622, and each heat-resistant conveyer belt is driven to rotate by a transmission carrier roller and a driven carrier roller, for example, the No. 1 heat-resistant conveyer belt 614 is driven by the transmission carrier roller 6141 to drive a gear transmission belt 629 to rotate, and drives the No. 1 heat-resistant conveyer belt 614 to rotate together with the driven carrier roller 6142. Meanwhile, in the process, under the action of the draught fan 907 and the axial flow fan 625, the waste heat air flow in the waste heat conveying pipe 908 connected with the outlet of the draught fan 907 of the cyclone separator 9 is introduced into the vertical hot air inlet main pipe 6241 of the hot air distributor 624, as shown in fig. 10, passes through the transverse secondary air distribution pipe 6242 and the longitudinal tertiary air distribution pipe 6243 of the grate-type hot air distributor 624, and is uniformly distributed into the bottom of the pre-drying chamber 631 by the small air distribution round holes 6244 on each air distribution pipe, and moves upwards as the hot air flow, and the wet straw primary crushed short material on each heat-resistant conveying belt is blown by the small round holes 6143 of each heat-resistant conveying belt to float between the two adjacent heat-resistant conveying belts in a weak fluidization manner, the flow direction of the wet material is opposite to that of the hot air flow and is in a countercurrent contact manner, the gas-solid heat transfer is intensified, the drying speed is accelerated, and the moisture content of the material on the lowest heat-resistant conveying belt is minimum, the hot air entering from the lower end has the highest air speed and the highest temperature, so that the straws are more easily fluidized and float, and the drying effect is better. Meanwhile, the rising low-temperature and humid air is filtered by the dust filter 613 at the uppermost end of the pre-drying chamber 631 and finally discharged from the exhaust chimney 612, so that the pollution to the environment is reduced to the maximum extent.
(4) Secondary drying of the straw sections: as shown in fig. 1 and 2, the straw segment material discharged from the discharge port 626 of the pre-drying chamber 631 of the belt pre-drying device 6 falls onto the wet straw lifting conveyor 7, is lifted and conveyed to the screw feeder 802 at the left end of the screw drying device 8, and is further conveyed to the screw drying chamber 801 for secondary drying. During the drying process, natural air blown in by an air blower 807 is heated by an electric heater 806, enters the distribution of a hot air distributor 805, tangentially flows into a spiral drying chamber 801 in the stirring direction of an electric stirring device, and spirally rises to blow straw particles falling from the middle position of the spiral drying chamber 801 from a spiral feeder 802 to be fluidized, the flow direction of the semi-dry material is opposite to that of hot air flow and is in countercurrent contact, so that the gas-solid phase heat transfer is intensified, the drying speed is accelerated, the fluidized layer of the straw particles upwards moves along with the loss of moisture, and when the semi-dry material moves to the uppermost end of the spiral drying chamber 801, the semi-dry material is discharged from a hot air outlet 803 and tangentially rotates into a cyclone separator 9 through a feed inlet 901 of the connected cyclone separator 9 to be subjected to gas-solid separation. The waste heat air after gas-solid separation is discharged from the air-bleed port 902 at the upper end and is added into the pre-drying chamber 631 of the pre-drying device 6 again through the waste heat delivery pipe 908 for pre-drying the wet straw material, and the trace fine powder brought by the waste heat air falls into the No. 1 collecting bin 10 after being filtered and trapped by the pipeline filter 903. The dry material after gas-solid separation falls into the bottom of the cyclone separator 9 and is discharged into a No. 2 aggregate bin 11 through a star discharger 904 and a discharge pipe 905. The dried materials in the No. 1 collecting bin 10 and the No. 2 collecting bin 11 are discharged into the discharging pipes 102 and 112 by the star-shaped dischargers 101 and 111, the discharging pipes 102 and 112 are communicated, and are powered by the axial flow fan 113 at the outlet of the discharging pipe 112, and the dried materials are fed into the No. 2 straw primary crushing material lifting and conveying air duct 12 and are lifted and conveyed into the No. 3 collecting bin 13 for collecting.
(5) Straw fine crushing and screening separation: as shown in FIG. 11, the dried material after the secondary drying of the straw segment passes through the 2 # primary crushed straw lifting and conveying air duct 12 and is lifted and conveyed into the 3 # collecting bin 13, and is discharged by the self-weight of the bottom L-shaped discharge port of the 3 # collecting bin 13, falls into the left end feed port of the sieving chamber 145 of the obliquely arranged and rotating sieving device 14 and enters the roller type rotary sieving chamber 145, the first transmission motor 141 is connected with the first rotating shaft 144 to rotate, the first rotating shaft 144 drives the star-shaped bracket 1452 fixed on the rotating shaft to rotate, the rotating shaft star-shaped bracket 1452 drives the sieving chamber 145 fixed on the star-shaped bracket 1452 to rotate, the material is rotated and centrifugally thrown down in the rotary sieving chamber 145 and moves downwards, and is contacted with the straw cutter set 159 which rotates reversely of the straw crushing device 15 and is arranged in the rear segment of the rotary sieving chamber 145 from left to right 1/4 coaxially, fine materials pass through a shell 1455 made of stainless steel screen meshes 1456 with a given aperture of the rotary screening chamber 145, pass through screening holes on the shell 1455, fall into the material sealed collection cover 16 right below for collecting, meanwhile, coarse materials continue to centrifugally drop and migrate downwards, continue to contact and be sheared and crushed in a staggered mode with a reverse rotating shearing cutter group of the straw fine crushing device 15 and a rack 1454 fixed on the cavity of the screening chamber 145 until the coarse materials are all cut into fine materials and all pass through the screening holes of the drum type rotary screening chamber to fall into the material sealed collection cover 16 right below, and a star-shaped discharger 1601 and a connecting hose 1602 which open a discharge port below the material sealed collection cover 16 discharge the materials into the No. 1 metering bin weighing device 17.
The operation steps of the straw fine crushing device 15 are as follows: the primary crushed straw entering the screening device 14 rotates and centrifugally drops along with the rotation of the rotary screening chamber 145, and moves downwards, and further enters the space of a straw fine crushing cutter set 159 of the straw fine crushing device 15, a fine crushing cutter set 1592 consisting of 4-8 shearing blades 15921 and a fine crushing cutter set 159 consisting of 10-50 fine crushing cutters 1592 which are fixed on a second rotating shaft 1594 rotate at a high speed under the driving of a second transmission motor 151, and further shear the primary crushed coarse straw into finer particles, the diameter size of the shearing cutters 1592 is alternately changed along the rotating shaft direction according to the large-small-large-small rule, and is matched with 4 teeth 1454 axially and uniformly distributed on the inner cavity of the rotary screening chamber 145 in a staggered manner, so that the shearing cutters 1592 can completely shear and thoroughly crush the material, crush the material into straw sections with the diameter of less than 5mm, and all pass through the screening holes of the rotary screening chamber 145, the material falling into the material sealing collection cover 16 directly below collects the materials. The second rotating shaft 1594 is connected with the second transmission motor 151 through a coupler 154, the second rotating shaft 1594 drives the fine crushing cutter group 159 to rotate through a transmission bearing 152 and a transmission bearing 155, and the fine crushing cutter group 159 is fixed on the second rotating shaft 1594 through a fine crushing cutter group initial positioning baffle 1591, a backing plate 1593 between cutters, a fine crushing cutter group tail end positioning baffle 1595, a shaft penetrating hole 15923, a shearing blade circumferential distribution fixing plate 15922 and other parts which are mutually matched, fastened and connected through a key groove 15924, a shaft key 15941 and a fastening nut 1596. The rotary screening chamber rear baffle 158 fixed on the second rotating shaft 1594 is hinged with a tail end flanging 1457 of a rotary screening chamber cavity housing 1455, meanwhile, the rotary screening chamber rear baffle 158 fixed on the rotating shaft 1594 is connected by the rotating shaft sleeve 157, the rotating shaft sleeve 157 is fixedly connected with the rear baffle 158 in a welding or fastening mode (static fit), the rotating shaft sleeve 157 is rotatably connected with the rotating shaft 1594 (dynamic fit), the axial direction of the rotary screening chamber and the steering of the fine crushing cutter set are not interfered with each other, the rotary screening chamber rear baffle can run independently and can rotate reversely, a high-speed effect is achieved at a low speed, and the effects of shearing, crushing and screening separation are enhanced.
(6) Ball milling and micro crushing: the straw sections with the length of less than 5mm are finely crushed by a straw fine crushing device 15, the discharged materials enter a No. 1 metering bin weighing device 17 for weighing, a certain amount of straw fine crushed materials are discharged by a star-shaped discharger 1706 and enter a left end screw feeder 181 of a horizontal ball mill micro-crushing device 18, the straw fine crushed materials are further fed by a screw feeder 181 and enter the horizontal ball mill micro-crushing device 18 for ball milling and micro-crushing, a rotary cylinder of the ball mill is in meshing transmission with a transmission large gear ring on the cylinder through a motor pinion by a transmission motor 182, when the discharge granularity of the crushed raw materials is less than 400 mu m, the ball milling is stopped, and the straw fine powder is discharged from a discharge port 183 of the ball mill. In the whole ball milling process, the rotating speed of the rotary cylinder is 10-50 r/min, the loading amount of the straw raw material is 10-15 Kg, the diameter of the copper balls is 10-15 mm, the ball milling time is 10-15 min, and the particle size of the straw powder can reach 75-400 mu m.
The second step is that: straw powder hydrolysis pretreatment:
the straw fine powder prepared by the first step ball milling is discharged into a straw powder lifting and conveying air duct 19 connected with a ball mill discharge port 183, and is lifted and conveyed into a No. 4 material collecting bin 20 by the conveying air duct 19, is discharged into a No. 2 metering bin weighing device 21 through a star discharger 203 at the lower end of the conveying air duct, is weighed by a certain amount, is discharged into a feed port 221 of a screw extrusion straw hydrolyzing machine 22 through a star discharger 218 at the lower end of the conveying air duct, and is driven by a transmission motor 223 to rotate at a certain rotating speed, so that the straw powder is brought into the screw extrusion machine 222 for hydrolysis. In the hydrolysis process, firstly, a hot water pump 2408 of a # 1 heater 24 is started to enable hot water at 50-60 ℃ in a heating water tank 2401 to sequentially pass through a water outlet control valve 2409, the hot water pump 2408 and a coil heat exchanger water inlet control valve 2407 to enter a coil heat exchanger 225 wound on a machine body of a screw extruder 222, materials in the screw extruder 222 are heated to about 50 ℃ through heat exchange, and liquid after the heat exchange is controlled by a coil heat exchanger water return control valve 2406 to enter the heating water tank 2401 through a water return port 2405 to be heated and recycled. Meanwhile, in the hydrolysis process, the prepared liquids in the No. 1 ingredient storage tank 231, the No. 2 ingredient storage tank 232 and the No. 3 ingredient storage tank 233 in the No. 1 liquid-phase ingredient storage tank group 23 are slowly added into the screw extruder 222 through a discharge valve 2315 at the lower end of each prepared liquid storage tank and a precision metering pump (not shown), and the prepared liquids in the No. 1 ingredient storage tank 231, the No. 2 ingredient storage tank 232 and the No. 3 ingredient storage tank 233 are respectively a lubricating additive, a hydrolysis main catalytic acid and a cocatalyst acid with certain concentration dosage. After the hydrolysis is finished after the heat preservation and hydrolysis are carried out for 10min at the given screw rotating speed, the hydrolyzed materials are discharged by a star discharger 226 at the tail end of the screw extruder 222 and enter a screw extrusion modification reaction unit 26 for modification reaction.
In the second step of straw powder hydrolysis pretreatment process, the No. 1 heater 24 heating is not needed, the screw strong extrusion and strong shearing action of the screw extruder is directly utilized, the mechanical energy is converted into heat energy, the temperature of the material is slowly increased, the hydrolysis time is prolonged, and the hydrolysis is finished after 15min at a certain screw rotating speed.
S2: primary oxidation-sulfonation esterification modification of straw lignocellulose:
the method is carried out in a screw extrusion modification reaction unit, and the specific process is as follows:
the hydrolyzed material is discharged by a star discharger 226 at the tail end of a screw extrusion straw hydrolyzing machine 22, enters a feed inlet 2611 of a No. 1 screw extruder 261 of a screw extrusion modification reaction unit 26 at the lower end, and is fed into a zigzag screw extrusion modification reaction unit 26 formed by connecting the No. 1 screw extruder 261, the No. 2 screw extruder 262, the No. 3 screw extruder 263 and the No. 4 screw extruder 264 in series by a rotating screw 2614 to be subjected to primary oxidation-sulfonation esterification modification. In the modification reaction process, firstly, 50-60 ℃ water in the No. 2 heater 28 is started to heat the material to about 50 ℃ through the coil heat exchanger heating machine body, and then the preparation liquid in the No. 2 liquid-phase ingredient storage tank group 25 is added in sequence. As shown in fig. 22, the material first enters the # 1 screw extruder 261, and meanwhile, the oxidant with a certain concentration dose in the # 1 ingredient storage tank 251 in the # 2 liquid-phase ingredient storage tank group 25 is slowly added into the # 1 screw extruder 261 through the discharge three-way valve 2514 in cooperation with the precision metering pump; after the oxidation chain scission reaction is carried out for a certain time, discharging the mixture through a discharge control valve 2612 of a No. 1 screw extruder into a No. 2 screw extruder 262, and slowly adding an acidic sulfonating agent with a certain concentration in a No. 2 ingredient storage tank 252 into the No. 2 screw extruder 262; after the sulfonation reaction is carried out for a certain time, the mixture is discharged through a discharge control valve of a No. 2 screw extruder and enters a No. 3 screw extruder 263 and a No. 4 screw extruder 264 for further oxidation and sulfonation reaction, and after the heat preservation reaction is carried out for a certain time, a black straw lignocellulose one-time oxidation-sulfonation esterification modified pasty viscous material (lignocellulose sulfonate, mainly cellulose sulfonate) is obtained, discharging the materials through a star discharger 266 at the tail end of a 4 # screw extruder 264, feeding the materials into a 3 # metering bin weighing device 29, metering and weighing the materials, feeding the materials into a straw dissolving tank 30, a certain amount of deionized water or tap water in a water tank 31 is added into the straw dissolving tank 30, after preliminary dissolution under the low-speed stirring of the stirring device, the materials are discharged through crab claw type discharge pipes 301 around the bottom of the straw dissolution tank 30 and enter a reaction kettle group 33 with the lower end in an annular matrix distributed structure. The process is an intermittent continuous propulsion operation process of intermittent feeding and discharging, and after materials in each kettle reach the required weight, the reaction kettle group is opened to carry out secondary oxidation-sulfonation esterification modification treatment on the straw lignocellulose.
In the primary oxidation-sulfonation esterification modification reaction process, a No. 2 heater 28 is not needed for heating, the screw strong extrusion and strong shearing effects of a screw extruder are directly utilized, mechanical energy is converted into heat energy, the temperature of the material is slowly increased, other operating conditions are the same, and compared with a heating mode, the modification time in each screw extruder is prolonged by 5min under a certain screw rotating speed in a non-heating mode.
In the primary oxidation-sulfonation esterification modification reaction process, 2 methods can be adopted with respect to the power transmission portion of the screw extrusion modification reaction unit 26. The method comprises the following steps: each screw extruder is independently used by a respective transmission motor, 4 screw extruders are arranged in a zigzag series, the adjacent screw extruders run in reverse directions, the No. 1 screw extruder 261 and the No. 3 screw extruder 263 run in the counterclockwise direction, the No. 2 screw extruder 262 and the No. 4 screw extruder 264 run in the clockwise direction, and the feeding direction of each screw is matched with the rotating direction of the motor; the second method comprises the following steps: the method adopts a grouping form, the No. 1 screw extruder 261 and the No. 3 screw extruder 263 are an A group, the No. 2 screw extruder 262 and the No. 4 screw extruder 264 are a B group, the A group is driven by a transmission motor 267 through a transmission belt 265, the B group is driven by a transmission motor 268 through a transmission belt 269, the rotating directions of the A group and the B group are opposite, and the feeding direction of each screw is matched with the rotating direction of the motor.
In the primary oxidation-sulfonation esterification modification reaction process, in relation to the heating heat transfer part of the screw extrusion modification reaction unit 26, tap water is injected into a heating water tank 2801 of a2 # heater 28 through a raw water inlet 2803, is heated by a heating wire 2811, hot water passes through a water outlet control pipe valve 2809 and a hot water pump 2808 in sequence, enters an external heating coil heat exchanger water inlet control valve 2807 of a 3 # screw extruder 263 as a starting point, passes through 3 # screw extruders, 2 # screw extruders and 1 # screw extruders in sequence, flows in a direction opposite to the direction of straw materials, is subjected to countercurrent radiation heat exchange, finally passes through an external heating coil heat exchanger water return control valve 2806 of a 1 # screw extruder 261 as an end point, passes through a water return port 2805, and enters the heating water tank 2801 again for secondary heating and recycling. The # 2 heater 28 also includes a thermometer 2802, a manhole 2804 and a sewage outlet 2810, which facilitates the temperature measurement, maintenance and waste water discharge of the heater.
S3: secondary oxidation-sulfonation esterification modification of straw lignocellulose:
the reaction is carried out in a reaction kettle group 33, and the specific process is as follows: s2 sulfonated materials with lower degree of substitution after primary oxidation-sulfonation esterification modification of straw lignocellulose are weighed by a 3 # weighing bin 29, discharged into a straw dissolving tank 30, added with water for preliminary dissolution, discharged into a reaction kettle group 33 with an annular matrix distributed structure right below, and when the materials in each kettle reach the required weight, the reaction kettle group 33 is started to carry out secondary sulfonation esterification modification treatment of the straw lignocellulose. As shown in fig. 23, firstly, the deionized water of about 50 ℃ in the # 1 ingredient storage tank 271 in the # 3 liquid-phase ingredient storage tank group 27 is started, a certain amount of deionized water is added into the reaction tank group, and the mixture is stirred at a low speed to be uniformly mixed to prepare a base solution with a certain concentration; then the 55-60 ℃ water in the 3 # heater is started to heat the body of the reaction kettle through the coiled pipe type heating pipe 33054 to heat the materials to about 50 ℃, then other prepared liquid in the 3 # liquid phase ingredient storage tank group 27 is added in sequence, firstly the oxidant with certain concentration and dosage in the 2 # ingredient storage tank 272 in the 3 # liquid phase ingredient storage tank group is slowly added into the reaction kettle group through the liquid discharge control valve 2723, the 1 # main liquid discharge control valve 2771 and the 2 # main liquid discharge control valve 2782 in cooperation with the precision flowmeter 2781, after stirring and oxidizing reaction for a certain time, the alkali liquor with certain concentration and dosage in the 3 # ingredient storage tank 273 in the 3 # liquid phase ingredient storage tank group is added according to the same flow control mode, after the pH value is stirred and adjusted to be 7.5-8.0, the sulfonating agent with certain concentration and dosage in the 4 # ingredient storage tank 274 in the 3 # liquid phase ingredient storage tank group is added, after heat preservation and stirring sulfonation reaction for a certain time, obtain a secondary sulfonated and esterified modified material (lignocellulose sulfonate mainly comprising lignin sulfonate).
S4: hydroxymethylation-etherification modification of straw lignocellulose:
the method is carried out in a reaction kettle group, and the specific process is as follows: adding a certain concentration and dosage of hydroxymethylation reagent in a 5 # batching storage tank 275 in a 3 # liquid-phase batching storage tank group into the secondary oxidation-sulfonation esterification modification liquid of the straw lignocellulose obtained in the step S3 in the reaction kettle group according to the same flow control mode, stirring the hydroxymethylation reagent for a certain time, finally adding a certain concentration and dosage of etherifying agent in a 6 # batching storage tank 276 in the 3 # liquid-phase batching storage tank group, preserving the temperature, stirring the etherifying reagent for a certain time, and naturally cooling the etherifying reagent to the normal temperature to obtain a certain concentration of light brown straw lignocellulose ester-etherified sticky liquid water reducer with high sulfonation degree and high etherification degree, namely the obtained product. The drain pump of the reactor group is turned on and the product is discharged into the finished product storage tank group 34.
S5: storage and anti-settling cycle of the product:
the process is carried out in the finished product tank group 34, and the specific process is as follows: as shown in fig. 24 and 25, the water reducing agent product prepared in the reaction kettle group 33 is pumped into the finished product tank group annular liquid inlet main pipe 3405 directly above the finished product tank group 34 under the action of the liquid outlet pump 3307 of the reaction kettle group 33, and is discharged into the finished product tank group 34 distributed in an annular matrix form by a plurality of tank group liquid inlet branch pipes 3403 distributed on the annular liquid inlet main pipe 3405, and under the action of the tank group high-level communication pipe valve 3404 and the tank group low-level communication pipe valve 2, the liquid level is filled into each finished product tank of the finished product tank group 34, and the liquid outlet pump 3307 and each liquid inlet pipe valve 3308 of the reaction kettle group 33 are stopped and closed, and the product is kept stand to be used or sold. When the finished product storage tank group 34 is placed for a period of time and precipitates appear at the lower ends of the storage tanks, a circulating liquid discharge pump 3410 arranged at the periphery of the lower end of the finished product storage tank group 34 is started, liquid discharge port pipe valves on the storage tanks communicated with a ring-shaped liquid discharge main pipe 3409 at the lowest end of the finished product storage tank group 34 are opened, the precipitated liquid at the lower parts of the storage tanks of the finished product storage tank group 34 enters the ring-shaped liquid discharge main pipe 3409, and then is pumped into a circulating liquid inlet main pipe 3405 of the finished product storage tank group through a circulating liquid discharge pump 3410 connected with the ring-shaped liquid discharge main pipe 3409, a plurality of circulating liquid inlet branch pipes 3402 distributed on the circulating liquid inlet main pipe 3405 of the finished product storage tank group are discharged into the corresponding storage tanks of the finished product storage tank group 34. And continuously and circularly discharging liquid from the bottom and continuously and circularly feeding liquid from the top of the finished product storage tank group 34, and after the liquid in the finished product storage tank group 34 is circulated for a period of time, uniformly mixing the liquid, dissolving and dissolving the precipitate, and stopping circulation. Or when the product is used or sold, the circulating system is started to uniformly mix the products in the finished product storage tank group 34, and then the mixed products are discharged through the discharge pipe valve 3407 of the finished product storage tank group 34.
The invention relates to the function, composition and working principle of a measuring bin weighing device, taking the schematic diagram of the assembly structure of a No. 2 measuring bin weighing device 21 and a No. 4 collecting bin 20 in figure 20 as an example, the explanation is as follows: the device has the functions of accurately weighing the weight of the slightly crushed straw, putting the slightly crushed straw into the spiral extrusion straw hydrolysis machine 22 for hydrolysis of straw powder, controlling the adding amount of the material and ensuring the hydrolysis quality of the straw. The installation form is suspension type installation. The weighing device 21 of the measuring bin consists of a measuring bin 211, a hanging bracket fixing plate supporting frame 212, a platform scale/platform scale supporting platform fixing hanging bracket 213, a hanging bracket fixing plate 214, a measuring bin feeding hole 215, a platform scale/platform scale 216, a platform scale/platform scale supporting platform 217, a star discharger 218 and a connecting hose 219. In order to meet the requirements of the process, the platform balance/platform balance 216 is placed on a platform balance/platform balance supporting platform 217, the supporting platform 217 is suspended and fixed through a platform balance/platform balance supporting platform fixing hanger 213, the fixing hanger 213 is welded or hinged and fixed on a hanger fixing plate 214 at the upper end, and the hanger fixing plate 214 is supported on a supporting frame 212; the measuring bin 211 is fixed on a scale/platform 216, the upper feed inlet 215 of the measuring bin 211 is movably connected with a connecting hose 204 at the lower end of a collecting bin 202 of a 4 # collecting bin 20 on a fixing plate 214, and a star discharger 203 at the lower end of the collecting bin 202 is fixedly connected with the connecting hose 204; the star discharger 218 at the lower end of the metering bin 211 is fixedly connected with a connecting hose 219; the connecting hose 219 can be movably connected or closely contacted with a receiving device at the lower end thereof, such as a container or a material conveying belt. The measuring bin 211 is fixed on the platform scale/platform scale 216, the upper connecting hose 204 and the lower connecting hose 219 well play a role in connecting the logistics pipelines of the upper equipment and the lower equipment, and can eliminate the influence of the external force of the upper equipment and the lower equipment on the weighing precision of the measuring bin weighing device 21, and the adding, reducing, accumulating and zero clearing operations are performed, so that the calculation of the input amount of the materials is facilitated.
The present invention will be described with reference to the following examples;
the straw raw materials used in the examples are wheat straw and corn straw harvested in the Tianshui area of Gansu province of 2018 and cotton straw harvested in Xinjiang, the harvested straws are air-dried, the dry straws including stems and leaves are crushed and ground to obtain fine powder, and the fine powder is subjected to composition content analysis and detection of lignin, hemicellulose, cellulose and the like, and the analysis results are shown in the following table 1 in terms of dry substances and mass fraction%.
TABLE 1 analysis and detection data of straw composition content (% by mass)
Figure 627285DEST_PATH_IMAGE001
Example 1
A preparation method of an ester ether sulfonated composite water reducing agent based on straw modification comprises the following specific steps:
s1: the straw raw material pretreatment comprises the following specific processes:
the first step is as follows: pre-crushing, cleaning, drying, fine crushing and micro-crushing the straw raw material:
after a certain amount of raw material straw bundles 3 are naturally air-dried, the raw material straw bundles are firstly crushed into straw sections of about 1-3 cm through a straw primary crushing device 2; the discharged materials are lifted and conveyed to a cleaning device 5 through a No. 1 straw primary crushed material lifting and conveying air duct 4 to clean impurities such as mud and sand in the discharged materials; then, after primary drying by a pre-drying device 6, discharging the materials, falling on a straw primary crushed material lifting conveyer belt 7, further lifting and conveying the materials into a spiral dryer 8 for secondary drying, enabling the water content of the straws to be below 10 percent, calculating according to mass percent, entering a cyclone separator 9 for gas-solid separation, and enabling the straws to fall into a No. 1 collecting bin 10 and a No. 2 collecting bin 11 for collection; the collected straw discharge materials enter a No. 2 straw primary crushing material lifting and conveying air duct 12 for lifting and conveying, enter a rotary screening device 14, are further crushed and screened by the rotary screening device 14 and a straw fine crushing device 15, and are sieved to obtain straw fine crushed materials with the particle size of less than 5 mm; weighing the straw fine crushed materials by a weighing device 17 of a measuring bin, controlling the weight, putting the weighed materials into a horizontal ball mill micro crushing device 18 for ball milling and micro crushing, controlling the granularity of the crushed materials to be below 400 mu m after ball milling, stopping ball milling, and discharging.
The straws are rich wheat straws in northwest regions. The hot air used by the pre-drying device 6 comes from the waste heat air discharged from the screw dryer 8. The air temperature of the pre-drying device 6 is 50-70 ℃. The air temperature of the spiral dryer 8 is 120-150 ℃, and the air temperature is increased through electric heating. The ball mill is a horizontal ball mill, the particle size of the straw raw material is less than 5mm, the rotating speed is 10-50 r/min, the loading amount of the raw material is 15 Kg, the ball loading amount is 1500, 1000 copper balls with the diameter of 10mm and 500 copper balls with the diameter of 15mm are arranged, the ball milling time is 15min, and the particle size of the obtained powder is 75-400 mu m.
The second step is that: straw powder hydrolysis pretreatment:
the straw powder prepared by the first ball milling is lifted and conveyed to a No. 4 collecting bin 20 through a straw powder lifting and conveying air duct 19, and discharged from the No. 4 collecting bin 20, enters a No. 2 metering bin weighing device 21, is weighed by 15000g, and is fed into a screw extrusion straw hydrolysis machine 22 for hydrolysis. In the hydrolysis process, firstly, 50-60 ℃ water in a No. 1 heater 24 is started to heat materials to about 50 ℃ through a coil heat exchanger heating machine body, then the flow is controlled to slowly add the prepared liquid in No. 1, No. 2 and No. 3 prepared liquid storage tanks in a No. 1 liquid-phase prepared storage tank group 23 into a spiral extrusion straw hydrolysis machine 22, the No. 1, No. 2 and No. 3 prepared liquid are respectively a lubricating additive, a hydrolysis main catalytic acid and a cocatalyst acid with certain concentration and dosage, after the heat preservation hydrolysis is carried out for 10min at a certain screw rotating speed, the hydrolysis is finished, and a star discharger at the tail end of the spiral extrusion straw hydrolysis machine 22 discharges the materials into a spiral extrusion modification reaction machine group 26 to carry out modification reaction.
The lubricating additive is oleic acid, and the solid-to-solid ratio of the straw to the oleic acid is 1000 g to 10 ml. The main hydrolysis catalytic acid is acrylic acid represented by monocarboxylic acid, and the solid-acid ratio of the straw to the acrylic acid is 1000 g: 30 ml; the hydrolysis catalysis-assisting acid is dilute sulfuric acid with the mass concentration of 30 g/L, and the solid acid ratio of the straw to the dilute sulfuric acid is 1000 g: 100 ml; the screw extruder is a single/double screw extruder, and the rotating speed of the extruder is controlled to be 50-80 r/min.
S2: the method comprises the following specific steps of carrying out primary oxidation-sulfonation esterification modification on straw lignocellulose:
the straw material prepared by hydrolysis pretreatment of S1 straw powder is discharged into a No. 1 screw extruder of a screw extruder modification reaction unit 26 by a star discharger at the tail end of a screw extrusion straw hydrolysis machine 22, and the powder after hydrolysis of the straw is sent into a zigzag screw extrusion modification reaction 26 formed by connecting No. 1 to No. 4 screw extruders in series for primary oxidation-sulfonation esterification modification reaction by a rotating screw. In the reaction process, firstly, 50-60 ℃ water in the No. 2 heater 28 is started to heat the material to about 50 ℃ through the coil heat exchanger heating machine body, and then the preparation liquid in the No. 2 liquid-phase ingredient storage tank group 25 is added in sequence. The materials enter a No. 1 screw extruder, a liquid level control valve is matched with a precision flowmeter to control the flow, an oxidant with certain concentration and dosage in a No. 1 ingredient storage tank of a No. 2 liquid-phase ingredient storage tank group 25 is slowly added into the No. 1 screw extruder, the materials are discharged into the No. 2 screw extruder after oxidation chain scission reaction for certain time, an acid sulfonating agent with certain mass concentration and dosage in a No. 2 ingredient storage tank of the No. 2 liquid-phase ingredient storage tank group 25 is added, the materials are discharged into the No. 3 and No. 4 screw extruders for further oxidation and sulfonation reaction after sulfonation reaction for certain time, a black straw lignocellulose once oxidation-esterification modified pasty material is obtained after heat preservation reaction for certain time, the materials are discharged into a No. 3 ingredient weighing device 29 for weighing, then discharged into a straw dissolving tank 30, and a certain amount of deionized water or tap water in a water tank 31 is added into the straw dissolving tank 30, after preliminary dissolution under the low-speed stirring of the stirring device, the materials are discharged through crab claw type discharge pipes around the bottom of the straw dissolution tank 30 and enter a reaction kettle group 33 with the lower end in an annular matrix distributed structure. The process is an intermittent continuous propulsion operation process of intermittent feeding and discharging, and the reaction kettle group 33 is opened to carry out secondary sulfonation esterification and primary hydroxymethylation-etherification modification treatment on the straw lignocellulose after materials in each kettle reach the required weight.
The straw modified material is calculated by taking 15000g of the primary hydrolysis input amount of straw powder as a reference; the oxidant is hydrogen peroxide with the mass concentration of 10%, and the dosage is 3000 mL; the acidic sulfonating agent is sodium bisulfite with the mass concentration of 25 percent, and the dosage is 2000 g (1500 mL);
the screw extruder is a single screw extruder, and the rotating speed of a motor is controlled to be 50-80 r/min; the reaction lasts for a certain time, because of continuous operation, the modification reaction time of each batch of materials in a single screw extruder is the same, the heating time is 10min, and the total modification reaction time of a modification reaction unit consisting of 4 corresponding screw extruders is 40 min;
s3: the secondary oxidation-sulfonation esterification modification and the primary hydroxymethylation-etherification modification of the straw lignocellulose are specifically carried out by the following processes:
the sulfonated material with lower sulfonation degree obtained by primary oxidation-sulfonation modification of the straw lignocellulose in the screw extruder modification reaction unit 26, weighing 100Kg of discharged material by a 3 # weighing cabin weighing device 29 and feeding the discharged material into a straw dissolving tank 30, 150Kg of deionized water at about 50 ℃ in a water tank 31 is added into a straw dissolving tank 30, after the solution with the concentration of about 40 percent is prepared by preliminary dissolution under the low-speed stirring of a stirring device, the solution is sequentially discharged through crab claw type discharge pipes which are circumferentially distributed at the periphery of the bottom of a straw dissolution tank 30 and enters each reaction kettle of a reaction kettle group 35 with the lower end in an annular matrix distributed structure for secondary sulfonation esterification and primary hydroxymethylation-etherification modification treatment of straw lignocellulose, the feeding amount in each reaction kettle is required to be 250Kg, that is, the material dissolved in one time in the straw dissolving tank 30 can only satisfy the adding amount of one reaction kettle. The specific process is as follows:
firstly, opening deionized water with the temperature of about 50 ℃ in a No. 1 batching storage tank in a No. 3 liquid-phase batching storage tank group 27, adding 80Kg into each reaction kettle of a reaction kettle group 33, stirring at low speed to uniformly mix materials, and preparing a base solution with the concentration of 30%; then, opening 55-60 ℃ water in a No. 3 heater 32, heating the body of the reaction kettle by a coil heat exchanger to heat the materials to about 50 ℃, and then sequentially adding the prepared liquid in the No. 3 liquid-phase material preparation storage tank group 27; firstly adding an oxidant with a certain concentration and dosage in a No. 2 ingredient storage tank in a No. 3 liquid-phase ingredient storage tank group 27, stirring and oxidizing for a certain time, adding an alkali liquor with a certain concentration and dosage in a No. 3 ingredient storage tank in a No. 3 liquid-phase ingredient storage tank group 27, stirring and adjusting the pH value to 7.5-8.0, then adding a weakly alkaline sulfonating agent with a certain concentration and dosage in a No. 4 ingredient storage tank in a No. 3 liquid-phase ingredient storage tank group 27, stirring and sulfonating for a certain time, then adding a hydroxymethylating agent with a certain concentration and dosage in a No. 5 ingredient storage tank in a No. 3 liquid-phase ingredient storage tank group 27, stirring and hydroxymethylating for a certain time, finally adding an etherifying agent with a certain concentration and dosage in a No. 6 ingredient storage tank in a No. 3 liquid-phase ingredient storage tank group 27, preserving heat, stirring and etherifying for a certain time, naturally cooling to normal temperature, thus obtaining the straw sulfonated wood water reducing agent in light brown without precipitation, which the solid content is about 30%, the obtained product is marked as WHM-1.
Opening a liquid discharge branch pipe valve at the lower end of the No. 1 to No. 8 reaction kettles of the reaction kettle group 33, enabling the product to enter a circular liquid discharge main pipe arranged at the lowest end of the periphery of the reaction kettle group 33, starting a liquid discharge pump of the reaction kettle group 33, and discharging the product into a finished product storage tank group 34.
The amount of the primary sulfonated material added into each reaction kettle is 100Kg, and the addition amount of other materials is calculated by taking the amount as the reference; the oxidant is 30% hydrogen peroxide with the mass concentration of 3000 ml; the alkali liquor is sodium hydroxide with the mass concentration of 40%, the dosage is 6000 g (3500 mL), and the pH value of the solution is adjusted to 7.5; the sulfonating agent is sodium sulfite with the mass concentration of 50 percent, and the dosage is 2500 g (1250 mL); the hydroxymethylation reagent is formaldehyde solution with the mass concentration of 37%, and the dosage is 1300g (820 mL); the etherification reagent is 20% monochloroacetic acid solution, and the dosage is 2800 g (2250 mL); the rotating speed of a stirring motor of the reaction kettle is controlled to be 50-80 r/min; the reaction time in the oxidation, sulfonation, hydroxymethylation and etherification modification processes is 30min, and the total modification reaction time of the secondary ester etherification is 2 h.
S4: the storage and anti-precipitation circulation of the product comprises the following specific processes:
the water reducing agent product prepared in the reaction kettle group 33 is pumped into a finished product storage tank group annular liquid inlet main pipe right above a finished product storage tank group 34 under the action of a liquid outlet pump and a liquid outlet pipe valve of the reaction kettle group 33, liquid is discharged into the finished product storage tank group 34 in an annular matrix distribution mode formed by 1-4 finished product storage tanks through a plurality of storage tank group liquid inlet branch pipes distributed on the annular liquid inlet main pipe, the finished product storage tank group is filled with the liquid level under the action of a storage tank group high-level communication pipe valve and a storage tank group low-level communication pipe valve, the liquid outlet pump and each liquid inlet pipe valve of the reaction kettle group 33 are stopped and closed, and the product is stored in a standing mode. When the finished product storage tank group 34 is placed for a period of time and precipitates appear at the lower ends of the storage tanks, a circulating liquid discharge pump at the periphery of the lower end of the finished product storage tank group 34 is started, liquid discharge port pipe valves on the storage tanks communicated with an annular liquid discharge main pipe of the finished product storage tank group are opened, the precipitate liquid at the lower parts of the storage tanks of the finished product storage tank group 34 is pumped into the annular liquid discharge main pipe, then is pumped into a circulating liquid inlet main pipe of the storage tank group through a circulating liquid discharge pump discharge pipe valve connected with the annular liquid discharge main pipe and a storage tank group circulating liquid inlet main pipe control pipe valve, is discharged into corresponding storage tanks of the storage tank group through a plurality of finished product storage tank group circulating liquid inlet branch pipes distributed on the annular liquid inlet main pipe of the finished product storage tank group, is continuously circulated to discharge liquid and feed liquid from the bottom and the top of the storage tank group, after the circulation for a period of time, the water reducing agent in the storage tank group is uniformly mixed, and the precipitates are dissolved and disappear, the cycle is stopped. Or when the water reducing agent product is used or sold, the circulating system is started to uniformly mix the water reducing agent in the storage tank group, and then the water reducing agent is discharged through the discharge pipe valve of the finished water reducing agent storage tank group.
Example 2
A preparation method of an ester ether sulfonated composite water reducing agent based on straw modification comprises the following specific steps:
s1: the straw raw material pretreatment comprises the following specific processes:
the first step is as follows: pre-crushing, cleaning, drying, fine crushing and micro-crushing the straw raw material. The procedure was exactly as in example 1;
the second step is that: and (3) carrying out hydrolysis pretreatment on straw powder. The process is completely the same as example 1, except that the hydrolysis process does not require heating, the hydrolysis catalyst acid is added, and the hydrolysis time is different, which is specifically shown in the following:
the lubricating additive is stearic acid, and the solid-to-solid ratio of the straw to the stearic acid is 1000 g to 10 ml.
The main hydrolysis catalytic acid is dicarboxylic acid represented by itaconic acid, and the solid acid ratio of straw to itaconic acid is 1000 g: 20 ml;
the hydrolysis catalysis-assisting acid is dilute hydrochloric acid with the mass concentration of 30 g/L, and the solid acid ratio of the straw to the dilute hydrochloric acid is 1000 g: 100 ml;
in the hydrolysis process, the method adopts a non-heating mode, and the total hydrolysis time is 15 min.
S2: the specific process of the primary oxidation-sulfonation esterification modification of the straw lignocellulose is the same as that in the embodiment 1, the difference is that the added oxidant and sulfonating agent are different in dosage, and the materials do not need to be heated and have different reaction time, and the specific difference is as follows:
the oxidant is potassium permanganate solution with the molar concentration of 0.3M, and the dosage is 3500 ml;
the acidic sulfonating agent is chlorosulfonic acid solution with the mass concentration of 25%, and the dosage is 1500g (1100 mL);
the reaction lasts for a certain time, because of continuous operation, the modification reaction time of each batch of materials in a single screw extruder is the same, 15min is realized under the condition of no heating, and the one-time total modification reaction time of a modification reaction unit consisting of 4 corresponding screw extruders is 60 min;
s3: the specific processes of secondary oxidation-sulfonation esterification modification and primary hydroxymethylation-etherification modification of straw lignocellulose are the same as those in example 1, the differences are that the added oxidant, sulfonating agent and liquid alkali and the respective dosages thereof are different, the respective dosages of hydroxymethylation reagent formaldehyde and etherification reagent monochloroacetic acid are different, the final product is marked as WHM-2, and the specific differences are as follows:
the oxidant is potassium permanganate solution with the molar concentration of 1.0M, and the dosage is 2500 ml;
the alkali liquor is a sodium hydroxide solution with the mass concentration of 40%, the dosage is 7000 g (4200 mL), and the pH value of the feed liquid is 7.8;
the sulfonating agent is sodium sulfite solution with the mass concentration of 50%, and the using amount is 2000 g (1000 mL);
the hydroxymethylation reagent is a formaldehyde solution with the mass concentration of 37%, and the using amount is 1500g (950 mL);
the etherification reagent is monochloroacetic acid solution with the mass concentration of 20%, and the dosage is 2500 g (2000 mL);
example 3
A preparation method of an ester ether sulfonated composite water reducing agent based on straw modification comprises the following specific steps:
s1: the straw raw material pretreatment comprises the following specific processes:
the first step is as follows: pre-crushing, cleaning, drying, fine crushing and micro-crushing the straw raw material. The procedure was exactly as in example 1;
the second step is that: and (3) carrying out hydrolysis pretreatment on straw powder. The procedure is exactly the same as in example 1, with the difference that the hydrolysis catalyst acid is added, in particular: the lubricating additive is a mixture of 1/2 stearic acid and oleic acid, and the solid-to-solid ratio of the straw to the lubricating additive is 1000 g: 10 ml. The main hydrolysis catalytic acid is polycarboxylic acid represented by citric acid, and the solid acid ratio of the straw to the citric acid is 1000 g: 15 ml; the hydrolysis catalysis-assisting acid is a mixed acid with the mass concentration of 30 g/L dilute sulfuric acid and dilute hydrochloric acid accounting for 1/2 respectively, and the solid-acid ratio of the straw to the catalysis-assisting acid is 1000 g: 100 ml;
s2: the specific process of the primary oxidation-sulfonation esterification modification of the straw lignocellulose is the same as that in the example 1, and the difference is that the added oxidant and sulfonating agent are different in dosage, and the specific difference is as follows: the oxidant is hydrogen peroxide with the mass concentration of 10% and potassium permanganate solution with the molar concentration of 0.3M, and the dosage is 1900 ml respectively; the sulfonating agent is sulfamic acid solution with the mass concentration of 25%, and the dosage is 2400g (1800 mL);
s3: the specific processes of secondary oxidation-sulfonation esterification modification and primary hydroxymethylation-etherification modification of straw lignocellulose are the same as those in example 1, the differences are that the added oxidant, sulfonating agent and liquid alkali and the respective dosages thereof are different, the dosages of hydroxymethylation reagent formaldehyde and etherification reagent monochloroacetic acid are different, the final product is marked as WHM-3, and the specific differences are as follows:
the oxidant is hydrogen peroxide with the mass concentration of 30%, and the dosage is 3500 ml;
the alkali liquor is a sodium hydroxide solution with the mass concentration of 40%, the dosage is 8000g (4800 mL), and the pH value of the feed liquid is adjusted to 8.0;
the sulfonating agent is sodium sulfite solution with the mass concentration of 50%, and the using amount is 3000 g (1500 mL);
the hydroxymethylation reagent is a formaldehyde solution with the mass concentration of 37%, and the dosage of the hydroxymethylation reagent is 2000 g (1200 mL);
the etherification reagent is a monochloroacetic acid solution with the mass concentration of 20%, and the dosage is 3500 g (2800 mL);
comparative example 1
S1: the straw raw material pretreatment comprises the following specific processes:
the first step is as follows: preliminary crushing, cleaning and drying pretreatment of straw raw materials. The specific process is basically the same as the first step in S1 of example 1, except that the straw primary crushing device 2 in the first step in S1 of example 1 is crushed into straw sections of 1-3 cm as crushed straw, and the crushed straw is washed, dried and pretreated to be used as the crushed straw hydrolysis material in the second step.
The second step is that: and (3) carrying out hydrolysis pretreatment on the straw scraps. The specific procedure was exactly the same as in the second step of S1 of example 1, and was carried out in a screw-extruder hydrolyzer.
S2: the specific process of the primary oxidation-sulfonation esterification modification of the straw lignocellulose is completely the same as the S2 process in the example 1.
S3: the specific processes of secondary oxidation-sulfonation esterification modification and primary hydroxymethylation-etherification modification of the straw lignocellulose are completely the same as the S3 process in the embodiment 1.
The straw modified ester ether sulfonated composite water reducing agent with solid content of about 30 percent and a large amount of precipitates is obtained, and the final comparison product is marked as WHM-4.
Comparative example 2
S1: the straw raw material pretreatment comprises the following specific processes:
the first step is as follows: preliminary crushing, cleaning, drying and fine crushing pretreatment of the straw raw material. The specific process is basically the same as the first step S1 in example 1, except that the straw fragments with the size of less than 5mm obtained by crushing the straw in the first step S1 in example 1 by the fine crushing device 15 are used as the straw hydrolysis crushed material in the second step.
The second step is that: and (3) carrying out hydrolysis pretreatment on the straw scraps. The specific procedure was exactly the same as the second step in S1 of example 1.
S2: the specific process of the primary oxidation-sulfonation esterification modification of the straw lignocellulose is completely the same as the S2 process in the example 1.
S3: the specific processes of secondary oxidation-sulfonation esterification modification and primary hydroxymethylation-etherification modification of the straw lignocellulose are completely the same as the S3 process in the embodiment 1.
The straw modified ester ether sulfonated composite water reducing agent with solid content of about 30 percent and a large amount of precipitates is obtained, and the final comparison product is marked as WHM-5.
Comparative example 3
S1: the straw raw material pretreatment comprises the following specific processes:
the first step is as follows: pre-crushing, cleaning, drying, fine crushing and micro-crushing the straw raw material. The specific procedure was exactly the same as the first step in S1 of example 1.
The second step is that: the straw powder hydrolysis pretreatment is directly carried out in the reaction kettle group 33. Discharging straw powder prepared by ball milling in the first step from a discharge port of a ball mill, weighing 100Kg, and directly putting into a No. 1 reaction kettle in a reaction kettle group 33 for hydrolysis pretreatment, wherein the specific operation process is as follows: firstly, 230Kg of hot water at about 50 ℃ is added into a No. 1 reaction kettle of a reaction kettle group 33, water at 50-60 ℃ in a heater 38 is started to heat a No. 1 reaction kettle body through a coil heat exchanger to heat materials to about 50 ℃ and keep the temperature, under the condition of low-speed stirring of a stirring motor of the reaction kettle, hydrolysis main catalytic acid and auxiliary catalytic acid with certain concentration and dosage are added into the No. 1 reaction kettle of the reaction kettle group 33 through a feed inlet in sequence, the temperature is kept for hydrolysis for 60min, and the hydrolysis is finished;
the hydrolysis main catalytic acid and the hydrolysis auxiliary catalytic acid are completely the same as the second step mixture ratio in the S1 of the embodiment 1, and specifically comprise the following steps:
the main hydrolysis catalytic acid is acrylic acid, and the solid acid ratio of the straw to the acrylic acid is 1000 g: 30 ml;
the hydrolysis catalysis-assisting acid is dilute sulfuric acid with the mass concentration of 30 g/L, and the solid acid ratio of the straw to the dilute sulfuric acid is 1000 g: 100 ml;
the rotating speed of a stirring motor of the reaction kettle is controlled to be 50-80 r/min;
s2: the primary oxidation-sulfonation esterification modification of the straw lignocellulose is still directly carried out in the reaction kettle group 33, and the specific process is as follows:
in the feed liquid after hydrolysis pretreatment in the No. 1 reaction kettle of the second step reaction kettle group 33 of S1, firstly, slowly adding an oxidant with a certain concentration and dosage to perform oxidation chain scission reaction for 60min, then slowly adding an acidic sulfonating agent with a certain mass concentration and dosage to perform reaction for 60min under heat preservation and low-speed stirring, and finishing the primary oxidation-sulfonation esterification modification reaction;
the oxidant and the acidic sulfonating agent and the use amounts thereof are completely the same as those in S2 of example 1, specifically:
the input amount of the straw powder is 100Kg, and the addition amount of other materials is calculated by taking the input amount as a reference; the oxidant is 30% hydrogen peroxide by mass concentration, and the dosage is 6650 mL; the acidic sulfonating agent is 50% sodium bisulfite with the dosage of 6650 g (3325 mL);
s3: the secondary oxidation-sulfonation esterification modification and the primary hydroxymethylation-etherification modification of the straw lignocellulose are still directly carried out in the reaction kettle group 33, and the specific process is basically the same as that of S3 in the example 1, and specifically comprises the following steps:
firstly, slowly adding an oxidant with a certain concentration and dosage into feed liquid subjected to primary oxidation-sulfonation esterification modification of straw lignocellulose in a No. 1 reaction kettle of an S2 reaction kettle group 33, stirring and oxidizing for a certain time, then adding an alkali liquor with a certain concentration and dosage, stirring and adjusting the pH value to 7.5-8.0, then adding a weakly alkaline sulfonating agent with a certain concentration and dosage, stirring and sulfonating for a certain time, then adding a hydroxymethylating agent with a certain concentration and dosage, stirring and hydroxymethylating for a certain time, finally adding an etherifying agent with a certain concentration and dosage, keeping warm, stirring and etherifying for a certain time, standing and naturally cooling to normal temperature to obtain the straw-modified ester ether sulfonation type composite water reducing agent with light brown solid content and a large amount of precipitates, wherein the final contrast product is marked as WHM-6.
The oxidant, the liquid caustic soda, the sulfonating agent, the hydroxymethylating agent, the etherifying agent, the dosage and the reaction time of the oxidant, the liquid caustic soda, the sulfonating agent, the hydroxymethylating agent and the etherifying agent are all the same as those in S3 of the embodiment 1, and specifically the method comprises the following steps:
the oxidant is 30% hydrogen peroxide by mass concentration, and the dosage is 3000 ml;
the alkali liquor is sodium hydroxide with the mass concentration of 40%, the dosage is 6000 g (3500 mL), and the pH value of the feed liquid is adjusted to 7.5; the sulfonating agent is sodium sulfite with the mass concentration of 50 percent, and the dosage is 2500 g (1250 mL);
the hydroxymethylation reagent is formaldehyde solution with the mass concentration of 37%, and the dosage is 1300g (820 mL);
the etherification reagent is a monochloroacetic acid solution with the mass concentration of 20%, and the dosage is 2800 g (2250 mL);
the rotating speed of a stirring motor of the reaction kettle is controlled to be 50-80 r/min;
the reaction time in the oxidation, sulfonation, hydroxymethylation and etherification modification processes is 30min, and the total modification reaction time of the secondary ester etherification is 2 h.
And (3) determining the sugar content of the hydrolysate:
the hydrolysis effect comprises the following components by the total sugar content of hydrolysate: mannose, glucose, galactose and xylose arabinose are evaluation bases. The embodiment and the comparative example comprehensively consider the influence of the straw material granularity and the hydrolysis time on the straw hydrolysis effect in the straw pretreatment process.
Taking 1g of the hydrolyzed straw, adding 60ml of purified water for dissolving, stirring for 5min, taking out the slurry, separating on a centrifugal machine, centrifuging at the rotating speed of 500 r/min for 5min, and separating the supernatant for determining the content of reducing sugar and monosaccharide components. The content of soluble sugar is measured by a 3, 5-dinitrosalicylic acid method, and the influence of the straw material granularity and the hydrolysis time on the straw hydrolysis effect is evaluated. The remaining precipitate is unhydrolyzed straw lignocellulose and insoluble materials thereof, and is continuously used for modifying the subsequent straw lignocellulose.
The hydrolysis effects of examples 1 to 3 and comparative examples 1 to 3 are shown in Table 2.
TABLE 2 influence of grain size of straw powder and hydrolysis time on hydrolysis fructose content
Figure 449485DEST_PATH_IMAGE002
As can be seen from table 2: the grain size of the straw, the hydrolysis equipment and the hydrolysis time all have influence on the total sugar content of the hydrolysate. The hydrolysis effects of examples 1 to 3 were superior to those of comparative examples 1 to 3.
The straw is treated by ball milling, so that the size of the cellulose material can be obviously reduced, the ordered structure of cellulose crystals is further destroyed, the crystallinity of cellulose is reduced, the reaction surface is enlarged, the accessibility of the cellulose to chemical reagents is improved, the cellulose is more easily degraded by catalytic acid, the carbohydrate polymer is promoted to be converted into sugar, the smaller the particle size of the straw is, the more beneficial the straw hydrolysis is, the higher the total sugar content is, the shorter the hydrolysis time is, and the better the hydrolysis effect is.
As can be seen from Table 2, the hydrolysis effect in the screw extruder is far better than that in the conventional reaction kettle, which is represented by short hydrolysis time and high hydrolysis efficiency of the straw in the screw extruder. Screw extruders have a strong mixing capability and are typical "three pass one reverse" process intensification devices. After high-speed extrusion and strong shearing of the screw extruder, the particle size of the straw is further reduced, and in the extrusion process, great friction force is generated between the material and screw blades and between the material and the material, so that the material is crushed, cell walls are completely broken, lignin and cellulose are further separated, micropores of the lignocellulose are increased, the specific surface area is increased, and the accessibility of chemical reagents is further improved. The mechanical heat energy generated in the process of screw extrusion can raise the temperature of the material and accelerate the hydrolysis reaction. As the screw extrusion hydrolysis proceeds, the degraded lignocellulose generates a plurality of active sites which can be penetrated and decomposed by the solution continuously, the accessibility of the chemical agent is increased, and the degradation rate is increased.
As can be seen from table 2: for straw micro powder with the particle size of 75-400 mu m, the total sugar content of the hydrolysate tends to increase and decrease along with the extension of the hydrolysis time, and the hydrolysis time is 20min, which is a maximum value point. Certainly, the hydrolysis process of 1-3 cm and 1-10 mm straws can also have the phenomenon along with the prolonging of time, and only the time points are different. This is mainly due to: the extension of the screw extrusion hydrolysis time is detrimental to the degradation of lignocellulose, since over time some of the sugars are further converted to other products, resulting in a decrease in sugar content.
The organic acid main catalyst selected for straw hydrolysis can be used as a small molecular monomer required by the water reducing agent, particularly, the unsaturated carboxylic acid monomer is a raw material for synthesizing the polycarboxylic acid water reducing agent, and the unsaturated carboxylic acid monomer has water reducing performance, and the performance of the product is not influenced even if the unsaturated carboxylic acid monomer is slightly excessive. And the adverse effects of excessive chloride ions and sulfate ions brought by inorganic acid hydrochloric acid or sulfuric acid as hydrolysis acid, such as corrosivity and the like on the subsequent straw-based water reducing agent in the application of reinforced concrete, are reduced and avoided.
The corn straw, the cotton straw and the oil straw are used as raw materials, and the similar effects are achieved.
The hydroxyl of lignocellulose molecules in the straw and lignin and cellulose which are formed by reacting with reactive substances are sulfonated, esterified and etherified to form the modified ester ether sulfonated composite water reducing agent.
Application effects example:
and (3) performance testing: in order to verify the beneficial effects of the invention, the ester ether modified sulfonated straw-based water reducing agent prepared in the above examples 1, 2 and 3 and comparative examples 1, 2 and 3 was used as an experimental example to test the fluidity of cement paste, the slump and the expansion of concrete and the compressive strength of test pieces before and after the addition of the ester ether modified sulfonated straw-based water reducing agent. The cement is ordinary Portland cement P42.5R Gansu Qilianshan. Test method referring to GB/T8077-2012 'test method for homogeneity of concrete admixture' for testing fluidity and setting time of cement paste, W/C is 0.29, and when the folded solid content is 0.30wt%, the test result of fluidity of cement paste is shown in Table 3 relative to the cement dosage. Testing the slump, the expansion degree and the setting time of concrete according to GB/T50080-2002 standard of common concrete mixture performance test methods, and testing the compressive strength of a test piece according to GB/T17671-1999 cement strength test method, wherein the mineral powder is wine steel S95-grade mineral powder; the fly ash is second-grade ash; the sand is machine-made sand, and the fineness modulus of the medium sand is 2.6; the concrete is characterized in that stones with the particle size of 5-25 are adopted, and cement is adopted in the concrete according to the mass ratio of the components: ore sand: fly ash: sand: stone: the water content is 170: 90: 80: 810: 1070: 150, the rubber-sand ratio is 1: 3, adding a water reducing agent according to the proportion relative to the cement dosage when the folding and fixing dosage is 0.60wt%, wherein the stirring time is 180 seconds, and the vibrating time is 15 seconds; the glue-sand ratio is 1: 3, the concrete performance test results are shown in Table 4.
TABLE 3 Cement paste fluidity test results
Figure 760381DEST_PATH_IMAGE003
TABLE 4 concrete Performance test results
Figure 562115DEST_PATH_IMAGE004
As can be seen from table 3: the straw modified ester ether sulfonated composite water reducing agent prepared by the invention is used for the prepared cement paste, and has certain water reducing dispersion performance. The fluidity and the setting retarding effect performance of the cement paste of the embodiments 1 to 3 are obviously superior to those of the comparative examples 1 to 3, under the condition of low doping amount of 0.30%, the initial fluidity can reach 240mm, the fluidity in 60min can reach 210mm, the fluidity in 120min can reach about 180mm, and the good fluidity is shown in the aspect of the fluidity of the cement paste, so that the fluidity of the cement paste is larger, the time loss is small, compared with a blank sample, the initial setting time is at least prolonged by 120min, the final setting time is at least delayed by 240min, and the setting retarding effect is better.
As can be seen from table 4: the straw modified ester ether sulfonated composite water reducing agent is used for the prepared concrete and has certain water reducing dispersion performance. The cement paste water reducing rate, the fluidity, the compressive strength and other performances of the cement paste of the embodiments 1 to 3 are obviously superior to those of the comparative examples 1 to 3, under the condition of 0.60 percent of low mixing amount, the concrete shows good slump, the expansion degree and the compressive strength of a test piece, particularly compared with a blank sample, the initial setting time of the concrete is prolonged by at least 120min, the final setting time is delayed by at least 180min, the water reducing rate can reach more than 24 percent, the concrete has good initial and maintaining performances, has the advantages of delayed coagulation, higher water reducing rate, good workability, no bleeding and segregation phenomena, and accords with the long-distance conveying of commercial concrete engineering.
As can be further seen from tables 3 and 4: the influence of the straw particle size on the performance of cement paste prepared from the straw modified ester ether sulfonated composite water reducing agent and the performance of concrete is great, and the overall expression is as follows: the smaller the straw granularity is, the better the dispersion performance of the water reducing agent is, the higher the water reducing rate is, the better the fluidity is and the higher the pressure resistance is.
The smaller the straw granularity is, the better the straw hydrolysis effect is, the higher the total sugar content is, the better the delayed coagulation and water reduction effects of monosaccharide, polysaccharide and carboxylic acid are, the better the dispersing performance of the straw modified water reducing agent is, the higher the water reduction rate is, the better the fluidity is, and further the compressive strength of concrete is improved.
Before the straw is sulfonated and modified, oxidation chain scission reaction is carried out, so that a certain amount of functional groups meeting sulfonation activity are provided for the sulfonation process. With the increase of the using amount of the oxidant, the straw lignocellulose is cracked into a cracking product with smaller molecular weight, and the molecular chain of the cracking product has functional groups with reactive activity capable of generating active points of free radicals, such as-OH and-CH2The increase of the water reducing effect is better, the water reducing rate of the modified substance is improved, and the strength of the concrete is improved.
The straw sulfonation modification process adopts step sulfonation, firstly, a semi-dry method is adopted in a screw extrusion sulfonation modification reaction unit for primary oxidation-sulfonation modification, sulfonating agents suitable for an acidic system, such as chlorosulfonic acid, sulfamic acid and sodium bisulfite, are adopted as sulfonating agents to react with straw hydrolysis powder in a semi-dry method solid phase manner, mainly sulfonation is carried out on cellulose in the straw, lignin hardly participates in sulfonation in a weakly acidic environment, along with sulfonation, the acidity of hydroxyl in a straw cellulose molecular chain is weakened, the activity is reduced, the sulfonation rate of the straw cellulose is reduced, the substitution degree of the sulfonic group is lower, the water solubility of a product is not good, the water reducing performance is poor, and meanwhile, the pH value of the material is gradually increased; then the primary sulfonated modifier is subjected to secondary oxidation-sulfonation modification in a reaction kettle by a liquid phase method, and sodium sulfite (Na) suitable for a weak alkaline system is adopted2SO3) As sulfonating agent in aqueous solutionAnd under the alkalescent environment that liquid alkali is added to adjust the pH value to 7.5-8.0, the activity of phenolic hydroxyl which does not participate in lignin at the early stage is improved, the sulfonation rate of the lignin is accelerated, the sulfonation efficiency of the straw lignocellulose is finally improved, the substitution degree of sulfonic acid groups is further increased, and the water solubility of the product is increased.
When the secondary sulfonation is carried out in the reaction kettle, the material is carried out in the alkalescent environment with the pH value of 7.5-8.0, and the method is suitable for hydroxymethylation modification, so that the hydroxyl groups of the straw lignocellulose are increased, and the etherification modification of the lignocellulose is facilitated. Hydroxymethylation and etherification modification are carried out, so that the solubility of the modified material in water is increased, and the modified material has good water-reducing dispersibility.

Claims (6)

1. A preparation method of an ester ether sulfonated composite water reducing agent based on straw modification is characterized by comprising the following steps: the water reducing agent is prepared by sequentially carrying out primary oxidation-sulfonation esterification modification, secondary oxidation-sulfonation esterification modification and primary hydroxymethylation-etherification modification on hydrolyzed crop straws;
the hydrolyzed straw powder is obtained by hydrolyzing straw powder after pretreatment of primary crushing, cleaning, drying, fine crushing and micro crushing of crop straws, and specifically comprises the following two steps:
(1) the method comprises the following steps of pretreating straw raw materials by primary crushing, cleaning, drying, fine crushing and micro crushing, and comprises the following specific steps:
the first step is as follows: naturally drying the straw bundle, and crushing the straw bundle into straw sections of 1-3 cm;
the second step is that: cleaning the primarily crushed straw sections;
the third step: the cleaned straws are respectively and gradually dried to ensure that the moisture content of the straws is below 10 percent;
the fourth step: further crushing and screening the dried straw sections, and sieving to obtain straw fine crushed materials with the particle size of less than 5 mm;
the fifth step: carrying out ball milling and micro-crushing on the straw fine crushed material by using a ball mill, and controlling the discharge granularity below 400 mu m after ball milling to obtain straw powder;
(2) the straw powder is hydrolyzed, and the specific process is as follows:
the first step is as follows: feeding the straw powder prepared by ball milling pretreatment into a screw extrusion straw hydrolysis machine for hydrolysis;
the second step is that: in the hydrolysis process, firstly, heating the machine body to 50-60 ℃;
the third step: then slowly adding No. 1, No. 2 and No. 3 preparation solutions into a screw-extrusion straw hydrolyzing machine, wherein the No. 1, No. 2 and No. 3 preparation solutions are respectively a lubricating additive, a main hydrolyzing catalytic acid and a co-catalyzing acid, and performing heat preservation hydrolysis at a certain screw rotating speed to obtain straw hydrolyzing powder;
the lubricating additive is one or a combination of stearic acid and oleic acid, and the solid-to-solid ratio of the straw to the lubricating additive is 1000 g: 6-10 ml;
the hydrolysis main catalytic acid solution is one or a combination of more of monocarboxylic acid, dicarboxylic acid or polycarboxylic acid;
the solid acid ratio of the straw to the hydrolysis main catalytic acid is 1000 g: 10-30 ml, and the addition amount of the acid is released along with the unitary, binary and polybasic carboxylic acids+Sequentially reducing, wherein when the monocarboxylic acid is added, the solid acid ratio of the straw to the main catalytic acid is 1000 g to 30 ml; when dicarboxylic acid is added, straw: the solid acid ratio of the main catalytic acid is 1000 g to 20 ml; when the tricarboxylic acid is added, the solid acid ratio of the straw to the main catalytic acid is 1000 g to 15 ml;
the hydrolysis catalysis-assisting acid preparation solution is dilute sulfuric acid or dilute hydrochloric acid with the mass concentration of 30 g/L, and the solid-acid ratio of the straw to the hydrolysis catalysis-assisting acid is 1000 g: 100 ml;
feeding the straw hydrolysis powder into a screw extrusion modification reaction unit for modification reaction, wherein the modification is realized by the following steps:
(1) the primary oxidation-sulfonation esterification modification comprises the following specific steps:
the first step is as follows: feeding the hydrolyzed stalk powder into screw extruding modification reactor set comprising No. 1, No. 2, No. 3 and No. 4 screw extruders in serial connection;
the second step is that: in the modification reaction process, firstly, heating the machine body to heat the material to 45-55 ℃;
the third step: the straw hydrolysis powder firstly enters a No. 1 screw extruder, an oxidant is slowly added into the No. 1 screw extruder, and the straw hydrolysis powder is discharged and enters a No. 2 screw extruder after oxidation chain scission reaction for a certain time;
the fourth step: starting a new round of straw hydrolysis powder, feeding the straw hydrolysis powder into a No. 1 screw extruder, and repeating the third step to perform oxidation chain scission reaction;
the fifth step: feeding the No. 1 screw extruder into No. 2 screw extruder, adding acid sulfonating agent into No. 2 screw extruder, sulfonating for certain time, feeding into No. 3 and No. 4 screw extruder, further maintaining temperature, oxidizing and sulfonating for certain time to obtain black straw lignocellulose material, and feeding into straw dissolving tank;
and a sixth step: adding water into a straw dissolving tank, stirring, dissolving, and then adding into a reaction kettle for secondary sulfonation esterification and primary hydroxymethylation-etherification modification;
(2) the secondary oxidation-sulfonation esterification modification and the primary hydroxymethylation-etherification modification comprise the following specific processes:
the first step is as follows: firstly, deionized water with the temperature of 45-55 ℃ is added into a reaction kettle, and the materials are uniformly mixed by stirring at a low speed to prepare a base solution with a certain concentration;
the second step is that: then heating the body of the reaction kettle to heat the material to 55-60 ℃;
the third step: firstly, adding an oxidant, stirring for oxidation reaction for a certain time, adding an alkali liquor, stirring for adjusting the pH value to 7.5-8.0, then adding a weakly alkaline sulfonating agent, and stirring for sulfonation reaction for a certain time;
the fourth step: then adding a hydroxymethylation reagent, stirring for hydroxymethylation reaction for a certain time, finally adding an etherifying agent, preserving heat, stirring for reaction for a certain time, and naturally cooling to normal temperature to obtain the light brown straw lignocellulose ester ether sulfonated viscous liquid water reducing agent with a certain concentration, namely the product.
2. The preparation method of the ester ether sulfonated type composite water reducing agent based on straw modification according to claim 1, characterized in that: the ball milling adopts a horizontal ball mill, and the ball milling parameters are as follows: the particle size of the straw raw material is less than 5mm, the rotating speed is 10-50 r/min, the loading amount of the straw raw material is 10-15 Kg, the diameter of copper balls is 10-15 mm, the ball milling time is 10-15 min, and the particle size of discharged materials is 75-400 mu m.
3. The preparation method of the ester ether sulfonated composite water reducing agent based on straw modification according to claim 1 or 2, characterized by comprising the following steps: the screw-extrusion straw hydrolysis machine is a single/double screw extruder, and the rotating speed of a motor is controlled to be 50-80 r/min.
4. The preparation method of the ester ether sulfonated type composite water reducing agent based on straw modification according to claim 3, characterized by comprising the following steps: also included are storage and anti-settling cycles for the product, as follows:
the first step is as follows: pumping the water reducer product prepared in the reaction kettle group into an annular liquid inlet main pipe right above a finished product storage tank group, and discharging the water reducer product into each storage tank through liquid inlet branch pipes which are distributed on the annular liquid inlet main pipe and correspondingly connected with each storage tank, wherein the storage tanks are distributed in an annular matrix;
the second step is that: when the finished product storage tank is placed for a period of time and precipitates appear at the lower end of the finished product storage tank, a circulating liquid discharge pump arranged on the periphery of the lower end of the finished product storage tank set is started, the precipitated liquid at the lower part of each storage tank is pumped into an annular liquid discharge main pipe, the annular liquid discharge main pipe is communicated with the annular liquid inlet main pipe, liquid is discharged into a corresponding storage tank through liquid inlet branch pipes, liquid and top continuous circulating liquid inlet are performed from the bottom of the storage tank set, after the circulation is performed for a period of time, the water reducing agent liquid in the storage tank set is uniformly mixed, the precipitate is dissolved and disappears, and the circulation is stopped.
5. The ester ether sulfonated type composite water reducing agent based on straw modification prepared by the preparation method of claim 1, 2 or 3 is characterized in that: the straw modified ester ether sulfonated composite water reducing agent is applied to cement paste and concrete.
6. The ester ether sulfonated composite water reducing agent based on straw modification according to claim 5, characterized in that: in the case of 0.30% low addition of neat cement paste, the initial neat cement paste fluidity reaches 240mm, the 60min fluidity reaches 210mm, and the 120min fluidity reaches 180 mm.
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