CN101704643B - Method for producing concrete admixture by using coarse tall oil separated and refined slag - Google Patents
Method for producing concrete admixture by using coarse tall oil separated and refined slag Download PDFInfo
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- CN101704643B CN101704643B CN2009100447423A CN200910044742A CN101704643B CN 101704643 B CN101704643 B CN 101704643B CN 2009100447423 A CN2009100447423 A CN 2009100447423A CN 200910044742 A CN200910044742 A CN 200910044742A CN 101704643 B CN101704643 B CN 101704643B
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- tall oil
- slag
- residue
- concrete admixture
- oil separated
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- 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
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/16—Sulfur-containing compounds
-
- 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
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/34—Natural resins, e.g. rosin
-
- 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
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention discloses a method for producing concrete admixture by using coarse tall oil separated and refined slag, including the following steps: (1) deodorization of coarse tall oil separated and refined slag: adding 20-30% of hydrogen peroxide by mass concentration or 20-40% of potassium persulfate solution by mass concentration in the slag according to solid-to-liquid ratio of 1:0.3-0.5, and agitating for deodorization; (2) saponification of deodorized slag: putting the deodorized slag in a container, adding sodium hydroxide or sodium carbonate accounting for 20-40% of the slag mass and alcamines matters accounting for 2.0-10.0% of the slag mass, and agitating for saponification at 70-100 DEG C for 1.0-4h, the mass concentration of the obtain solution being controlled at 40-70%; and (3) compatibility and composition: lowering the temperature of the above solution to 50-70 DEG C, adding alpha-alkenyl sulphonate (AOS), sodium dodecyl sulfate (K12) and/or fatty alcohol-polyoxyethylene ether (AES) totaling 5-10% of the slag mass for fully dissolving to obtain pasty concrete admixture with mass concentration being 40-75%. The invention has low cost little doping, good application effect, easy transport and storage, and convenient construction operation.
Description
Technical field
The present invention relates to a kind of method of utilizing the coarse tall oil separated and refined slag modification to produce concrete admixture.
Background technology
Thick tall oil is one of sub product of kraft pine pulp mill; Though the composition variation range is bigger; But main content that it is generally acknowledged thick tall oil is resinous acid (having another name called sylvic acid), lipid acid; With a small amount of neutral substance and make oil have dark-coloured oxide compound, be widely used in making soap, lubricant, flotation agent, sizing agent, emulsifying agent, caking agent and paint, printing ink industry etc.
In kraft process, grease in the timber and resinous principle owing to the effect of alkali becomes soap, are dissolved in the black liquor, and neutral oil also is drawn out of and is dissolved in the soap lye simultaneously, Here it is sulfate soap.When black liquor was concentrated to finite concentration, sulfate soap just floated over above the black liquor.The sulfate soap of separating is the chocolate semi-fluid; The oil slick of oil-containing 50~55%wt; With saponified after the storagetank standing separation; And washings (with caustic soda, saltcake, salt or the like preparation) is sent to rinse bath together, alkaline washings can remove effectively saponified in 60~80% lignin and about 50% fiber and impurity.Washed saponified in the rinse bath with steam direct heating to 70 ℃; Be sent to the acidifying system again, decompose with acid (sulfuric acid, nitric acid or hydrochloric acid etc. all can), saponified and sour after reacting in the reactor drum; Resolve into components such as thick tall oil, lignin, fiber and gypsum, discharge H simultaneously
2S and CO
2Gas; These gases are sent to washer and wash, and then the mixture after the acidifying are sent to subsider separator standing sedimentation, because thick tall oil and xylogen density difference are little; Separate fully than difficulty; Collect the upper strata oil reservoir and can obtain the higher tall oil of purity, also be referred to as tall oil or Tall oil or Yatall MA, tall oil mainly is the mixture by resinous acid, lipid acid, neutrals and impurity.The content of each composition is different because of the difference of seeds, weather, the age of tree, conditions of cooking, separation condition.Thick tall oil of part and xylogen are then contained in the middle layer of separating; Owing to slightly tall oil and lignin separation are difficult, general enterprise separates the back with this part and sells peripheral little chemical enterprise with very low price, and recovery is the oil of remnants wherein; If amount is few; Then generally go out of use as rubbish, wasted resource, economic benefit is low.Orlop is a spent acid in three layers, after the separation, delivers to the spent acid groove to it, waits to add to supply to wash crude sulfate soap behind the alkali next time and use.
Air entrapment agent was applied to concrete existing more than 70 year.Air entrapment agent is a kind of tensio-active agent, can in the concrete whipping process, introduce many smallly and independent distribution is stable and lockedin air space, plays dispersed and wettability effect, thereby improves concrete workability, raising freeze-thaw-weather resistance and anti-permeability performance.Bubble structure in the concrete directly influences workability and freeze-thaw-weather resistance.The bubble that the high-quality air entrapment agent is introduced is spherical in shape, about 20~200 μ m of diameter, and spread ratio is less than 200 μ m.Usually, the concrete that starting material and wc are identical, air content is about 1.5% when mixing air entrapment agent, and number of freezing and thawing has only 15~25 times; And mix the concrete of high-quality air entrapment agent, and when aggregate size is 20~80mm, air content 3%~6% o'clock, number of freezing and thawing can reach more than 200 times.Micro-bubble plays lubrication as ball, its absorption again once more after also isolated water mud pellet disperses effectively, and cut off the capillary channel in the maturing, thus improved concrete workability, improve pumpability.In addition, bleed type water reducer can also further improve the water-reducing rate of concrete or mortar, reduces wc, remedy loss of strength with reduce the slump through the time loss.
The high-quality air entrapment agent can not only with compound uses such as multiple water reducer, frostproofer, pumping agent, and can with common use such as silica flour, flyash, ground slag, zeolite powder, swelling agent, reach the further purpose of improving concrete performance.Domestic air entrapment agent commonly used is broadly divided into two types at present:
1. rosin based air entrapment agent
The rosin based air entrapment agent mainly is that sylvic acid saponification thing and rosin become the ester class with condensation reactions at a certain temperature such as phenol, sulfuric acid, sodium hydroxide; Become than macromole through further polycondensation; Pass through sodium-hydroxide treatment again, become the polycondensate of sodium salt, i.e. colophonium pyrolytic polymer.This type air entrapment agent existing more than 70 year so far is widely used in pavement concrete, water conservancy project and polyacrylonitrile fiber concrete and some have the concrete works of antiseepage, freeze proof requirement.It is to improving concrete workability, water-retentivity, and it is remarkable to improve the weather resistance effect.But be difficult to dissolving, need heat, add alkali during use,, also need improve with shortcomings such as other admixture consistencies are relatively poor.
2. non-rosin based tensio-active agent
From the sixties in 20th century, begin development and use non-rosin based air entrapment agent, like air entrapment agents such as sulfo group Supragil GN, OP emulsifying agent, soap English powder, modified form AS 801,901A.The chemical structure characteristics of this type air entrapment agent are on the nonionic surfactant-based plinth, to introduce hydrophilic group, make it soluble in water, and whipability is good, and foam is thinner, and can be compound with other kind admixtures preferably, successfully are applied in the concrete for hydraulic structure engineering.Aniorfic surfactant such as sodium alkyl benzene sulfonate, soluble in water, be prone to bubble, but its foam is bigger, be prone to disappear.In addition, the oxyethylene affixture of non-ionics alkylphenol the bleed effect is also arranged, but price is higher.With three withered saponin(es is the air entrapment agent of staple, also in some engineerings, is applied in recent years.
In the Chinese commodity concrete construction, use more air entrapment agent to be mostly some ASs, principal item has rosined soap, colophonium pyrolytic polymer air entrapment agent, three obedient saponin(e air entrapment agents (is raw material with the plant Chinese honey locust), AS (mainly being sodium lauryl sulphate), sodium alkyl benzene sulfonate and polyethers and kinds of surface promoting agent mixture, acrylic acid epoxy ester resin synthesis type air entrapment agent, ZGK 5 concrete air-entrainer, high-performance sulfuric ester salt concrete air-entrainer and polycarboxylic acid concrete air-entrainer etc.
Alkali lignin and sulphonate thereof are a kind of ASs; Have diminishing, slow setting, foaming and dissemination, obtain using more widely in commerical ready-mixed concrete, pump concrete, water-proof concrete, concrete for hydraulic structure, road concrete, high-strength concrete (needing the control volume) as ordinary water-reducing agent usually.
Residue acid number behind the thick tall oil separation and purification is 120~140mg KOH/g, and resinous acid content is 44%~50%, and fatty acid content is 25%~30%, and unsaponifiable matter content is 11~15%, and alkali lignin content is 5.0%~8.0%.Utilize behind the thick tall oil separation and purification residue modification to produce concrete admixture and realized that not only thick tall oil oil refining separates the comprehensive utilization of back residue resource, solve the feedstream pollution problem of becoming estranged simultaneously again, and can reduce production costs, improve profit.The coarse tall oil separated and refined slag that utilization contains alkali lignin prepares concrete admixture; It is abundanter to have raw material sources; Cheap and product need not pass through the characteristics that just can directly use of separating; In actual production, have broad application prospects, make full use of promoting energy-saving and emission-reduction and resource, the protection environment has than important social and economic implications with the realization Sustainable development.
Summary of the invention
Technical problem to be solved by this invention provides that a kind of constructing operation is convenient, production efficiency is high, production cost is low, the eco-friendly method of utilizing coarse tall oil separated and refined slag to produce concrete admixture, to solve this type of residue complicated component, separation costs is high and is taken as usually that offal treatment is fallen or major defect such as low value utilization.
In order to solve the problems of the technologies described above, the method for utilizing coarse tall oil separated and refined slag to produce concrete admixture provided by the invention is characterized in that: adopt following steps:
(1), the deodorization of coarse tall oil separated and refined slag: in residue, adding mass concentration in solid (quality) liquid (volume) than 1: 0.3~0.5 ratio is that 20%~30% hydrogen peroxide or 20%~40% potassium persulfate solution stir deodorizing;
(2), the saponification of residue after the deodorization: the residue after the deodorization is put into container, add the sodium hydroxide (NaOH) or the yellow soda ash (Na that account for residue quality 20%~40%
2CO
3), and the alcamines material that accounts for residue quality 2.0%~10.0%, stir saponification at 70~100 ℃, the time is 1.0~4h, gained solution quality concentration is controlled at 40%~75%;
(3), compatibility is compound: the temperature of above-mentioned solution is reduced to 50~70 ℃; Add the α-Xi Jihuangsuanyan (AOS), sodium laurylsulfonate (K12) and/or the polyoxyethylenated alcohol sodium sulfate (AES) that account for residue quality 5%~10%; Fully dissolving obtains mass concentration and is 40% ~ 75% paste concrete admixture.
The paste concrete admixture that obtains in the above-mentioned steps (3) through spray drying process, then can be made solid, powdery type concrete admixture.
Described alcamines material is Monoethanolamine MEA BASF, diethylolamine or trolamine.
In the above-mentioned steps (3) temperature of solution reduced to after 50~70 ℃ and add XG 550, gelatin, gelatine or the gum arabic that accounts for residue quality 2%~5%.
As a kind of improvement of the present invention, the tall oil of being mentioned in (1) foregoing is also referred to as thick tall oil or Tall oil or Yatall MA; (2) raw material also can directly use thick tall oil to prepare concrete admixture; (3) after above-mentioned steps (3) is prepared the paste concrete admixture; Through drying meanss such as spraying dryings, then can make solid, powdery type concrete admixture, volume is 0.008%~0.01% in cement; Can be in concrete use separately, also can be used with other high efficiency water reducing agent etc.
Adopt the coarse tall oil separated and refined slag that utilizes of technique scheme to produce the method for concrete admixture; Because its complicated component and not segregative characteristics, adopt methods such as deodorization-saponification-compatibility is compound based on the residue behind the thick tall oil separation and purification, alleviate its unpleasant odor and the visual effect of improving residue; Solvability, foamy homogeneity and the stability of raising product and product are to the flexibility of cement; Can reach concrete water-reducing ratio >=6%, concrete 's air-containing reaches at 6%~8% o'clock, solved this type of residue because complicated component, not easily separated, go out of use or problem such as low value utilization; Cost of the present invention is low; Volume is few, is easy to transportation and keeping, and constructing operation is convenient.This product can improve concrete plasticity workability, and bleeding and segregation phenomenon are reduced greatly, significantly improves freeze-thaw resistance and watertightness, and concrete placing more is easy to do to and spares matter and densification.For the concrete admixture product of this type of residue production high added value has been opened up new approach.Therefore, this invention will produce good economy, society and environmental benefit, have excellent popularization and be worth.
Embodiment
Below in conjunction with specific embodiment the present invention is done further explain.
Embodiment 1:
(1), the deodorization of residue behind the thick tall oil separation and purification: ((it is that 30% superoxol stirs deodorization that the ratio than 1: 0.3 of volume/mL) adds mass concentration to the liquid of quality/g), carries out solid-liquid separation then by solid in residue; (2), the saponification of residue after the deodorization: the residue after the deodorization is put into container; Add 20% the sodium hydroxide of residue quality and the trolamine of residue quality 10%; Stir saponification at 90~100 ℃, the time is 1h, and gained solution quality concentration is controlled at 40%~75%; (3), compatibility is compound: above-mentioned solution temperature is reduced to 50~70 ℃, add the sodium lauryl sulphate (K12) that accounts for residue quality 10%, be mixed with solids content and be 40%~75% paste concrete admixture; (4), through drying means such as spraying drying, then can make solid, powdery type concrete admixture, the volume mass percent is 0.01% in cement, can in concrete, use separately, according to different needs, also can be used with other high efficiency water reducing agent etc.
Embodiment 2:
(1), thick tall oil separates the deodorization of back residue: ((adding of the ratio than 1: 0.4 mass concentration of volume/mL) is that 25% superoxol stirs deodorization to the liquid of quality/g), carries out solid-liquid separation then by solid in residue; (2), the saponification of residue after the deodorization: the residue after the deodorization is put into container; Add and account for the sodium hydroxide of residue quality 25% and 5% diethylolamine; Stir saponification at 80~90 ℃, the time is 2.0h, and gained solution quality concentration is controlled at 40%~75%; (3), compatibility is compound: above-mentioned solution temperature is reduced to 50~70 ℃, and adding accounts for the α-Xi Jihuangsuanyan (AOS) of residue quality 8% and 2% gelatine, is mixed with the paste concrete admixture of solids content 40%~75%; (4), through drying means such as spraying drying, then can make solid, powdery type concrete admixture, can in concrete, use separately, the volume mass percent is 0.009% in cement, according to different needs, also can be used with other high efficiency water reducing agent etc.
Embodiment 3:
(1), thick tall oil separates the deodorization of back residue: ((adding of the ratio than 1: 0.5 mass concentration of volume/mL) is that 40% potassium persulfate solution stirs to the liquid of quality/g), carries out solid-liquid separation then by solid in residue; (2), the saponification of residue after the deodorization: the residue after the deodorization is put into container; Add and account for the yellow soda ash of residue quality 30% and 2% Monoethanolamine MEA BASF; Stir saponification at 70~100 ℃, the time is advisable with 2h, and gained solution quality concentration is controlled at 40%~75%; (3), compatibility is compound: above-mentioned solution temperature is reduced to 50~70 ℃; Add and account for the polyoxyethylenated alcohol sodium sulfate (AES) of residue quality 10% and 5% gelatin; Can be mixed with the paste concrete admixture of solids content 40%-75%, the volume mass percent is 0.01% in cement; (4), through spray drying process, then can make solid, powdery type concrete admixture, can in concrete, use separately, according to different needs, also can be used with other high efficiency water reducing agent etc.
Embodiment 4:
(1), thick tall oil separates the deodorization of back residue: ((adding of the ratio than 1: 0.3 mass concentration of volume/mL) is that 30% superoxol stirs deodorization to the liquid of quality/g), carries out solid-liquid separation then by solid in residue; (2), the saponification of residue after the deodorization: the residue after the deodorization is put into container; Add and account for the sodium hydroxide of residue quality 25% and 5% trolamine; Stir saponification at 70~80 ℃, the time is 3.0h, and gained solution quality concentration is controlled at 40%~75%; (3), compatibility is compound: above-mentioned solution temperature is reduced to 50~70 ℃; The XG 550 that adds the polyoxyethylenated alcohol sodium sulfate (AES) account for residue quality 5%, 5% sodium lauryl sulphate (K12) and 3% is mixed with the paste concrete admixture of solids content 40%~75%; (4), through drying means such as spraying drying, then can make solid, powdery type concrete admixture, the volume mass percent is 0.09% in cement, can in concrete, use separately, according to different needs, also can be used with other high efficiency water reducing agent etc.
Embodiment 5:
(1), thick tall oil separates the deodorization of back residue: in residue, be that 30% superoxol stirs deodorization by the ratio adding mass concentration of solid (quality) liquid (volume) than 1: 0.3, carry out solid-liquid separation then; (2), the saponification of residue after the deodorization: the residue after the deodorization is put into container; Add and account for the sodium hydroxide of residue quality 25% and 5% trolamine; Stir saponification at 70~100 ℃, the time is 4.0h, and gained solution quality concentration is controlled at 40%~75%; (3), compatibility is compound: above-mentioned solution temperature is reduced to 50~70 ℃; The gum arabic that adds the α-Xi Jihuangsuanyan (AOS) account for residue quality 5%, 5% sodium lauryl sulphate (K12) and 3% is mixed with solids content and is 40%~75% paste concrete admixture; (4), through drying means such as spraying drying, then can make solid, powdery type concrete admixture, the volume mass percent is 0.008% in cement, can in concrete, use separately, according to different needs, also can be used with other high efficiency water reducing agent etc.
Claims (4)
1. method of utilizing coarse tall oil separated and refined slag to produce concrete admixture is characterized in that: adopt following steps:
(1), the deodorization of coarse tall oil separated and refined slag: in residue, adding mass concentration in the ratio of solid-to-liquid ratio 1: 0.3~0.5 is that 20%~30% hydrogen peroxide or 20%~40% potassium persulfate solution stir deodorizing; Solid is in quality g in the described solid-to-liquid ratio, and liquid is in volume mL;
(2), the saponification of residue after the deodorization: the residue after the deodorization is put into container; Add the sodium hydroxide or the yellow soda ash that account for residue quality 20%~40%; And the alcamines material that accounts for residue quality 2.0%~10.0%; Stir saponification at 70~100 ℃, the time is 1.0~4h, and gained solution quality concentration is controlled at 40%~75%;
(3), compatibility is compound: the temperature of above-mentioned solution is reduced to 50~70 ℃; Add the α-Xi Jihuangsuanyan, sodium laurylsulfonate and/or the polyoxyethylenated alcohol sodium sulfate that account for residue quality 5%~10%; Fully dissolving obtains mass concentration and is 40%~75% paste concrete admixture.
2. the method for utilizing coarse tall oil separated and refined slag to produce concrete admixture according to claim 1; It is characterized in that: the paste concrete admixture that obtains in the above-mentioned steps (3) through spray drying process, then can be made solid, powdery type concrete admixture.
3. the method for utilizing coarse tall oil separated and refined slag to produce concrete admixture according to claim 1 and 2, it is characterized in that: described alcamines material is Monoethanolamine MEA BASF, diethylolamine or trolamine.
4. the method for utilizing coarse tall oil separated and refined slag to produce concrete admixture according to claim 1 and 2 is characterized in that: in the above-mentioned steps (3) temperature of solution reduced to and add XG 550, gelatin, gelatine or the gum arabic that accounts for residue quality 2%~5% after 50~70 ℃.
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CN108793814A (en) * | 2018-07-17 | 2018-11-13 | 四川银凯新材料有限公司 | A kind of preparation method of air entraining agent |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
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CN1107814A (en) * | 1994-12-01 | 1995-09-06 | 王令久 | Efficient mortar additive |
CN1807333A (en) * | 2006-02-16 | 2006-07-26 | 江苏博特新材料有限公司 | Concrete air-entrainer |
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CN1107814A (en) * | 1994-12-01 | 1995-09-06 | 王令久 | Efficient mortar additive |
CN1807333A (en) * | 2006-02-16 | 2006-07-26 | 江苏博特新材料有限公司 | Concrete air-entrainer |
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