CN102010148B - Method for producing naphthalene series water reducing agent and aliphatic water reducing agent - Google Patents
Method for producing naphthalene series water reducing agent and aliphatic water reducing agent Download PDFInfo
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Abstract
The invention discloses a method for producing a naphthalene series water reducing agent and an aliphatic water reducing agent, which comprises the following steps of: melting industrial naphthalene and methyl naphthalene, adding concentrated sulfuric acid and sulfur trioxide to perform sulfonation reaction, performing hydrolysis by adding water after the reaction is finished, then adding aqueous solution of formaldehyde to perform condensation reaction, and finally, adding sodium hydroxide to neutralize the reaction solution till the pH value is 7 to 9 so as to obtain the naphthalene series water reducing agent; and in the sulfonation reaction, reclaiming sulfur dioxide in the reaction system by using the aqueous solution of sodium hydroxide to obtain sodium sulfite reclaimed solution or mixed reclaimed solution of sodium sulfite and sodium hydrogen sulfite, adding acetone and formaldehyde into the reclaimed solution in turn, and obtaining the aliphatic water reducing agent after the reaction is finished. The high-cost industrial naphthalene is replaced by using low-cost methyl naphthalene or wash oil in the method, and the quality of the prepared naphthalene series water reducing agent reaches Chinese quality standard GB8076-2008; and the method solves the problem of sulfur dioxide waste gas utilization, reduces the cost for producing the aliphatic water reducing agent, changes waste into valuable, and has the characteristics of energy conservation and environmental friendliness.
Description
Technical field
The present invention relates to build concrete water reducer preparation field, especially relate to the method for a kind of coproduction naphthalene water reducer and aliphatic water reducing agent.
Background technology
Concrete admixture has become five big composition components of modern concrete material, and water reducer is most important and the most frequently used concrete admixture.High efficiency water reducing agent is claimed superplasticizer again, and staple is an AS, mainly is through improving the character at solid, liquid interface, significantly reducing the workability that the fresh concrete water consumption still keeps concrete mix simultaneously.
China begins the research of synthetic manufacturing of naphthalene series high-efficiency water-reducing agent and application performance the initial stage seventies from 20 worlds; Successively succeed in developing UNF-5; (CN87104392.0 CN94115574.0), and obtains widespread use in industries such as buildings to the high efficiency water reducing agent product of FDN series; But, cause its production cost constantly to increase because it is in short supply day by day to produce the starting material-NAPTHALENE FLAKES. (INDUSTRIAL GRADE of naphthalene water reducer.Simultaneously; Produce naphthalene water reducer and generally adopt sulfuric acid sulfonation; The problem that thereupon is accompanied by be exactly sodium sulfate along with temperature Change, solubleness also exists difference, generally adopts neutralize oversaturated sodium sulfate or in sulfonation process, bring out the reduction sodium sulphate content to acid mist with organic band aqua of lime at present; Reclaim and the organic band aqua of recycle, the consequent is that the loaded down with trivial details and cost of operation is constantly soaring again.In addition, in sulfonation process, can produce a large amount of by product sulfurous gas, sulfurous gas causes very big pollution (pressurization of sulfurous gas transforms, Deng Yongjia, Li Xuerong, sulfuric acid industry, 2001 (2)) to environment; Simultaneously, produce naphthalene water reducer raw material Components of Wash Oil more complicated commonly used, except naphthalene and verivate thereof, also contain a large amount of micromolecular compounds; These micromolecular compounds are highly volatile in the sulfuric acid sulfonation process, and carries a large amount of sulfurous gas and discharge outside the still, has caused very big pollution (with coal tar washing oil synthesizing efficient water reducer and performance analysis thereof to production environment; Xu Zifang, Zhang Mingxu, Zhu Zongjun; Environmental engineering, 2010,28 (1)).
Aliphatic water reducing agent is after 20th century, studied successfully the nineties, because its water-reducing rate height, the simple environmental protection of production process, sodium sulfate and advantage such as chloride ion content is low and cost is cheap had relatively obtained widespread use in recent years at home.Publication number discloses a kind of method of manufacture of sulfonated acetone-formaldehyde condensation products for the CN1066448A patent documentation; It mainly is the method that in sulfonation process, adopts base catalysis; At present, do not had and utilize the waste water that forms in the naphthalene water reducer production process directly as the report of the raw materials for production of aliphatic water reducing agent.
Summary of the invention
The invention provides the method for a kind of coproduction naphthalene water reducer and aliphatic water reducing agent; This method environmental friendliness; Realized the comprehensive utilization of sulfonation waste water simultaneously, naphthalene water reducer that this method prepares and aliphatic water reducing agent are the important water reducer of building trade.
The method of a kind of coproduction naphthalene water reducer and aliphatic water reducing agent comprises:
(1) in closed reactor, NAPTHALENE FLAKES. (INDUSTRIAL GRADE is warming up to 120～160 ℃, adding mass percent concentration is the vitriol oil more than 95%; Feed sulphur trioxide; Reaction is more than 0.5 hour, and sulphur trioxide reacts completely, and opens vacuum unit then; With enclosed system insulation reaction 2～4h under 140～170 ℃ of conditions, the total acidity (vitriolic mass percentage content in the solution) of reacting to solution is 22%～34%; Simultaneously the gas in the reaction system is evacuated in the absorption unit that aqueous sodium hydroxide solution is housed; Prepare recovery solution; Wherein said absorption unit is that an end is communicated with closed reactor, the vacuum unit that the other end is communicated with the container that aqueous sodium hydroxide solution is housed;
(2) under 100～160 ℃ of conditions, add entry in the closed reactor in step (1), insulation reaction 10～40min, hydrolysis reaction to solution total acidity (vitriolic mass percentage content in the solution) is 19%～30% then;
(3) reaction mixture that obtains in the step (2) is cooled to 60～95 ℃, adds formaldehyde solution, condensation reaction is 4～8 hours under 100～130 ℃ of conditions;
(4) after condensation reaction was accomplished, the pH value that adding liquid caustic soda (sodium hydroxide) is neutralized to reaction mixture was 7～9, obtained naphthalene water reducer through spraying drying;
(5) the recovery solution that obtains in the step (1) is joined in another reaction vessel, under 20～50 ℃ of conditions, add acetone then, stir more than the 0.5h, add formaldehyde solution then, be warming up to 90～105 ℃ then, react and obtained aliphatic water reducing agent in 2～5 hours.
In the above-mentioned steps, step (1)～(4) are for producing the step of naphthalene water reducer, and wherein the mass ratio of institute's processing industry naphthalene and the vitriol oil, sulphur trioxide and formaldehyde solution is 1: 0.1～0.9: 0.1～0.9: 0.4～0.7 in step (1) and the step (3); The mass ratio of the NAPTHALENE FLAKES. (INDUSTRIAL GRADE that adds in water that adds in the step (2) and the step (1) is 0.3～0.8: 1; The preparation process of naphthalene water reducer is shown below:
For the NAPTHALENE FLAKES. (INDUSTRIAL GRADE of saving in the cost step (1) also can be replaced by the mixture of NAPTHALENE FLAKES. (INDUSTRIAL GRADE and washing oil or the mixture of NAPTHALENE FLAKES. (INDUSTRIAL GRADE and methylnaphthalene, the reaction process of methylnaphthalene is similar with the reaction process of naphthalene; If when adopting the mixture replacement NAPTHALENE FLAKES. (INDUSTRIAL GRADE of NAPTHALENE FLAKES. (INDUSTRIAL GRADE and washing oil mixture or NAPTHALENE FLAKES. (INDUSTRIAL GRADE and methylnaphthalene, each component can be arbitrarily than mixing in the mixture, preferably in the mixture content of NAPTHALENE FLAKES. (INDUSTRIAL GRADE greater than 10% less than 100%.When being replaced by the mixture of the mixture of NAPTHALENE FLAKES. (INDUSTRIAL GRADE and washing oil or NAPTHALENE FLAKES. (INDUSTRIAL GRADE and methylnaphthalene like NAPTHALENE FLAKES. (INDUSTRIAL GRADE, the mass ratio of the institute's processing industry naphthalene mixtures (mixture of the mixture of NAPTHALENE FLAKES. (INDUSTRIAL GRADE and washing oil or NAPTHALENE FLAKES. (INDUSTRIAL GRADE and methylnaphthalene) and the vitriol oil, sulphur trioxide and formaldehyde solution is 1: 0.1～0.9: 0.1～0.9: 0.4～0.7 in step (1) and the step (3); The mass ratio of the NAPTHALENE FLAKES. (INDUSTRIAL GRADE mixture (mixture of the mixture of NAPTHALENE FLAKES. (INDUSTRIAL GRADE and washing oil or NAPTHALENE FLAKES. (INDUSTRIAL GRADE and methylnaphthalene) that adds in water that adds in the step (2) and the step (1) is 0.3～0.8: 1.
The sulfonation reaction of naphthalene or methylnaphthalene is an electrophilic substitution reaction, when temperature is low (35～60 ℃) to obtain product mainly be α-Nai Huangsuan or alpha-methyl-naphthalene sulfonic acid; When temperature is higher, then mainly generate beta-naphthalenesulfonic-acid or beta-methylnaphthalene sulfonic acid.And the condensation reaction of naphthene sulfonic acid or methyl naphthalene sulfonic acid and formaldehyde is a cationoid reaction; When having electron withdrawing groups such as sulfonic group on the naphthalene nucleus, can reduce the reactive behavior of naphthalene nucleus; When α-Nai Huangsuan or alpha-methyl-naphthalene sulfonic acid and formaldehyde condensation, steric hindrance is unfavorable for the carrying out of condensation reaction more greatly; Beta-naphthalenesulfonic-acid or beta-methylnaphthalene sulfonic acid is presence bit inhibition effect not then, so in the sulfonation reaction step, should control reaction conditions reaction is carried out towards the direction that generates beta-naphthalenesulfonic-acid or beta-methylnaphthalene sulfonic acid; Experiment shows that vitriol oil concentration helps generating beta-naphthalenesulfonic-acid or beta-methylnaphthalene sulfonic acid more greatly more, so the concentration of the preferred vitriol oil is more than or equal to 98%; The control of temperature of reaction also helps beta-naphthalenesulfonic-acid in addition or beta-methylnaphthalene sulfonic acid generates, and preferred temperature of reaction is 140～170 ℃.
The purpose of hydrolysis is that α-Nai Huangsuan that generates or alpha-methyl-naphthalene sulfonic acid are removed in the step (2).
Step (5) is for utilizing the process of the recovery solution production aliphatic water reducing agent that produces in the above-mentioned production naphthalene water reducer process.
Can produce a large amount of sulfurous gas in the sulfonation process, in the step (1) sulphur trioxide fed reaction system after, for preventing vacuum unit unreacted sulphur trioxide is taken away, can at first guarantee more than sulphur trioxide reaction half a hour; Through reaction and conversion; Almost no longer contain sulphur trioxide in the gas; And then utilize vacuum unit to utilize sodium hydroxide to absorb the sulfurous gas that produces in the sulfonation process; PH through control sodium hydroxide absorption liquid to be to obtain the mixture of sodium sulfite aqueous solution or S-WAT and aqueous solution of sodium bisulfite, preferably reclaims solution and be the pH value and be 4～9, mass percent concentration is 20～40% S-WAT and the mixed aqueous solution of sodium sulfite anhy 96 or pH value are 9～12, mass percent concentration is 10～94% sodium sulfite aqueous solution; When utilizing above-mentioned recovery formulations prepared from solutions aliphatic water reducing agent, the mass ratio of acetone and formaldehyde solution is preferably 1: 0.1～and 0.4: 0.3～0.7.
The NAPTHALENE FLAKES. (INDUSTRIAL GRADE that method adopted of coproduction naphthalene water reducer of the present invention and aliphatic water reducing agent, washing oil, methylnaphthalene and other reagent of using or solvent all can adopt the commercially available prod.
The method of coproduction naphthalene water reducer of the present invention and aliphatic water reducing agent adopts methylnaphthalene, the expensive NAPTHALENE FLAKES. (INDUSTRIAL GRADE of washing oil instead of part cheaply, and the naphthalene water reducer quality of processing can reach Chinese quality standard GB8076-2008; Simultaneously, solved admittedly useless aftertreatment problem, and form waste gas of sulfur dioxide also obtains rational recycling, reduced production aliphatic water reducing agent cost, turned waste into wealth, had the characteristics of energy-saving and environmental protection.
Description of drawings
Fig. 1 is the process flow sheet of the method for coproduction naphthalene water reducer of the present invention and aliphatic water reducing agent.
Embodiment
The process flow sheet of the coproduction naphthalene water reducer of the present invention and the method for aliphatic water reducing agent is as shown in Figure 1.
Embodiment 1
Each material by mass ratio is: NAPTHALENE FLAKES. (INDUSTRIAL GRADE and washing oil mixing raw material: sulfuric acid: sulphur trioxide: hydrolysis water: formaldehyde solution=1: 0.84: 0.21: 0.45: 0.59, (mass ratio of NAPTHALENE FLAKES. (INDUSTRIAL GRADE and washing oil mixture=1: 1).In the sulfonation reaction pot, add NAPTHALENE FLAKES. (INDUSTRIAL GRADE 1kg and washing oil 1kg mixing raw material, behind the heating and melting; When continuing to be warming up to 120 ℃; The sulfuric acid 1.68kg that adds concentration 98%; Feed sulphur trioxide 420g and carry out sulfonation reaction 0.5h; Sulphur trioxide is opened vacuum absorption device after fully reacting, sulfur dioxide gas body and function aqueous sodium hydroxide solution that vacuum is pulled out absorb prepare that the pH value is 9～10, mass percent concentration is 25% sodium sulfite solution.Then with sulfonation reaction still internal reaction material be warming up to 145 ℃ the insulation 3h, react to the total acidity of solution be 30%; Be cooled to 125 ℃ then and add water 900ml, insulation 20min, the total acidity that is hydrolyzed into solution is 24%; Be discharged in the condensation pot, controlled temperature to 78 ℃ added formaldehyde solution (specifications and models the are 36% commercial product) 1.2kg that mass percent concentration is and carries out condensation reaction, and formaldehyde solution finishes the sealed reaction pot, 100 ℃ of insulation reaction 5 hours; Insulation finishes to be discharged to the neutralization pot, and using liquid caustic soda to be neutralized to pH value is 7～8 promptly to get aqueous naphthalene water reducer, and liquid product process spraying drying is made the pulvis naphthalene water reducer.
With the mass percent concentration of above-mentioned preparation is that 25% sodium sulfite solution 1kg joins in the reactor; According to the quality of material ratio be: sodium sulfite solution: acetone: formaldehyde solution=1: 0.19: 0.5 in the time of 30 ℃ ± 2 ℃, adds 190g acetone; Stir half a hour; Slowly drip formaldehyde solution 500g, the dropping formaldehyde time drips within 2.5h and finishes, and is warming up to 100 ℃ of insulations and promptly gets aliphatic water reducing agent in 2.5 hours.
Embodiment 2
Each material by mass ratio is: NAPTHALENE FLAKES. (INDUSTRIAL GRADE and washing oil mixing raw material: sulfuric acid: sulphur trioxide: hydrolysis water: formaldehyde solution=1: 0.32: 0.58: 0.4: 0.59, (mass ratio of NAPTHALENE FLAKES. (INDUSTRIAL GRADE and washing oil mixture=9: 1).In the sulfonation reaction pot, add NAPTHALENE FLAKES. (INDUSTRIAL GRADE 0.9kg and washing oil 0.1kg mixing raw material, behind the heating and melting; When continuing to be warming up to 120 ℃; The sulfuric acid 0.32kg that adds concentration 98%; Feed sulphur trioxide 0.58kg and carry out sulfonation reaction 1h; Sulphur trioxide is opened vacuum absorption device after fully reacting, sulfur dioxide gas body and function aqueous sodium hydroxide solution that vacuum is pulled out absorb prepare that the pH value is 10～11, mass percent concentration is 94% sodium sulfite solution.Then with sulfonation reaction still internal reaction material be warming up to 145 ℃ the insulation 3h, react to the total acidity of solution be 32%; Be cooled to 125 ℃ then, add water 400ml, insulation 20min, the total acidity that is hydrolyzed into solution is 25%; Be discharged in the condensation pot, controlled temperature to 78 ℃ added formaldehyde solution (specifications and models are 36% a commercial product) 0.59kg and carries out condensation reaction, and formaldehyde solution finishes the sealed reaction pot, 100 ℃ of insulation reaction 5 hours; Insulation finishes to be discharged to the neutralization pot, and using liquid caustic soda to be neutralized to pH value is 8～9 promptly to get aqueous naphthalene water reducer, and liquid product process spraying drying is made the pulvis naphthalene water reducer.
With above-mentioned mass percent concentration is that to be prepared into mass percent concentration be that 25% sodium sulfite solution 1kg joins in the reactor for 94% sodium sulfite solution; According to the quality of material ratio be: sodium sulfite solution: acetone: formaldehyde solution=1: 0.1 8: 0.49 in the time of 30 ℃ ± 2 ℃, adds 180g acetone; Stirred 1 hour; Slowly drip formaldehyde solution 490g, the dropping formaldehyde time drips within 3h and finishes, and is warming up to 100 ℃ of insulations and promptly gets aliphatic water reducing agent in 3 hours.
Embodiment 3
Each material by mass ratio is: NAPTHALENE FLAKES. (INDUSTRIAL GRADE and washing oil mixing raw material: sulfuric acid: sulphur trioxide: hydrolysis water: formaldehyde solution=1: 0.84: 0.21: 0.45: 0.59, (mass ratio of NAPTHALENE FLAKES. (INDUSTRIAL GRADE and washing oil mixture=1: 9).In the sulfonation reaction pot, add NAPTHALENE FLAKES. (INDUSTRIAL GRADE 0.1kg and washing oil 0.9kg mixing raw material, behind the heating and melting; When continuing to be warming up to 120 ℃; The sulfuric acid 0.84kg that adds concentration 98%; Feed sulphur trioxide 210g and carry out sulfonation reaction 1h; Sulphur trioxide is opened vacuum absorption device after fully reacting, sulfur dioxide gas body and function concentration hydrogen aqueous solution of sodium oxide that vacuum is pulled out absorb prepare that the pH value is 7～8, mass percent concentration is 25% S-WAT and sodium sulfite anhy 96 mixing solutions.Then with sulfonation reaction still internal reaction material be warming up to 145 ℃ the insulation 3h, react to the total acidity of solution be 33%; Be cooled to 125 ℃ then and add water 450ml, the total acidity that is hydrolyzed into solution is 27%, insulation 20min; Be discharged in the condensation pot, controlled temperature to 78 ℃ added formaldehyde solution (specifications and models are 36% a commercial product) 590g and carries out condensation reaction, and formaldehyde solution finishes the sealed reaction pot, 100 ℃ of insulation reaction 5 hours; Insulation finishes to be discharged to the neutralization pot, and using liquid caustic soda to be neutralized to pH value is 7～8 promptly to get aqueous naphthalene water reducer, and liquid product process spraying drying is made the pulvis naphthalene water reducer.
With the mass percent concentration of above-mentioned preparation is that 25% S-WAT and sodium sulfite anhy 96 mixing solutions 1kg join in the reactor; According to the quality of material ratio be: sodium sulfite solution: acetone: formaldehyde solution=1: 0.2: 0.53 in the time of 30 ℃ ± 2 ℃, adds 200g acetone; Stirred 0.5 hour; Slowly drip formaldehyde solution 530g, the dropping formaldehyde time dripped within 2.5 hours and finishes, and was warming up to 100 ℃ of insulations and promptly got aliphatic water reducing agent in 2.5 hours.
Embodiment 4
Each material by mass ratio is: NAPTHALENE FLAKES. (INDUSTRIAL GRADE and methylnaphthalene mixing raw material: sulfuric acid: sulphur trioxide: hydrolysis water: formaldehyde solution=1: 0.32: 0.58: 0.4: 0.59, (mass ratio of NAPTHALENE FLAKES. (INDUSTRIAL GRADE and methylnaphthalene mixture=3: 2).In the sulfonation reaction pot, add NAPTHALENE FLAKES. (INDUSTRIAL GRADE 0.6kg and methylnaphthalene 0.4kg mixing raw material, behind the heating and melting; When continuing to be warming up to 120 ℃; The sulfuric acid 320g that adds concentration 98%; Feed sulphur trioxide 580g and carry out sulfonation reaction 1h; Sulphur trioxide is opened vacuum absorption device after fully reacting, sulfur dioxide gas body and function concentration hydrogen aqueous solution of sodium oxide that vacuum is pulled out absorb prepare that the pH value is 6～7, mass percent concentration is 40% S-WAT and sodium sulfite anhy 96 mixing solutions.Then with sulfonation reaction still internal reaction material be warming up to 145 ℃ the insulation 3h, react to the total acidity of solution be 34%; Be cooled to 125 ℃ then and add water 400ml, the total acidity that is hydrolyzed into solution is 27%, insulation 20min; Be discharged in the condensation pot, controlled temperature to 78 ℃ added formaldehyde solution (specifications and models are 36% a commercial product) 590g and carries out condensation reaction, and formaldehyde solution finishes the sealed reaction pot, 100 ℃ of insulation reaction 5 hours; Insulation finishes to be discharged to the neutralization pot, and using liquid caustic soda to be neutralized to pH value is 8～9 promptly to get aqueous naphthalene water reducer, and liquid product process spraying drying is made the pulvis naphthalene water reducer.
With the mass percent concentration of above-mentioned preparation is that 25% S-WAT and sodium sulfite anhy 96 mixing solutions 1kg join in the reactor; According to the quality of material ratio be: sodium sulfite solution: acetone: formaldehyde solution=1: 0.19: 0.5 in the time of 30 ℃ ± 2 ℃, adds 190g acetone; Stirred 0.5 hour; Slowly drip formaldehyde solution 500g, the dropping formaldehyde time dripped within 3 hours and finishes, and was warming up to 100 ℃ of insulations and promptly got aliphatic water reducing agent in 3 hours.
Embodiment 5
Each material by mass ratio is: NAPTHALENE FLAKES. (INDUSTRIAL GRADE and methylnaphthalene mixing raw material: sulfuric acid: sulphur trioxide: hydrolysis water: formaldehyde solution=1: 0.60: 0.30: 0.80: 0.70, (mass ratio of NAPTHALENE FLAKES. (INDUSTRIAL GRADE and methylnaphthalene mixture=1: 4).In the sulfonation reaction pot, add NAPTHALENE FLAKES. (INDUSTRIAL GRADE 200g and methylnaphthalene 800g mixing raw material, behind the heating and melting; When continuing to be warming up to 120 ℃; The sulfuric acid 600g that adds concentration 98%; Feed sulphur trioxide 300g and carry out sulfonation reaction 0.5h; Sulphur trioxide is opened vacuum absorption device after fully reacting, sulfur dioxide gas body and function aqueous sodium hydroxide solution that vacuum is pulled out absorb prepare that the pH value is 6～7, mass percent concentration is 30% S-WAT and sodium sulfite solution.Then with sulfonation reaction still internal reaction material be warming up to 145 ℃ the insulation 3h, react to the total acidity of solution be 30%; Be cooled to 125 ℃ then and add water 800ml, insulation 20min, the total acidity that is hydrolyzed into solution is 28%; Be discharged in the condensation pot, controlled temperature to 78 ℃ added formaldehyde solution (specifications and models are 36% a commercial product) 700g and carries out condensation reaction, and formaldehyde solution finishes the sealed reaction pot, 100 ℃ of insulation reaction 5 hours; Insulation finishes to be discharged to the neutralization pot, and using liquid caustic soda to be neutralized to pH value is 7～8 promptly to get aqueous naphthalene water reducer, and liquid product process spraying drying is made the pulvis naphthalene water reducer.
With the above-mentioned mass percent concentration for preparing is that 25% S-WAT and sodium sulfite anhy 96 mixing solutions 1kg join in the reactor; According to the quality of material ratio be: sodium sulfite solution: acetone: formaldehyde solution=1: 0.21: 0.56 in the time of 30 ℃ ± 2 ℃, adds 210g acetone; Stir half a hour; Slowly drip formaldehyde solution 560g, the dropping formaldehyde time drips within 2.5h and finishes, and is warming up to 100 ℃ of insulations and promptly gets aliphatic water reducing agent in 2.5 hours.
Embodiment 6
Each material by mass ratio is: NAPTHALENE FLAKES. (INDUSTRIAL GRADE and methylnaphthalene mixing raw material: sulfuric acid: sulphur trioxide: hydrolysis water: formaldehyde solution=1: 0.40: 0.50: 0.6: 0.40, (mass ratio of NAPTHALENE FLAKES. (INDUSTRIAL GRADE and methylnaphthalene mixture=7: 3).In the sulfonation reaction pot, add NAPTHALENE FLAKES. (INDUSTRIAL GRADE 0.7kg and methylnaphthalene 0.3kg mixing raw material, behind the heating and melting; When continuing to be warming up to 120 ℃; The sulfuric acid 0.40kg that adds concentration 98%; Feed sulphur trioxide 0.50kg and carry out sulfonation reaction 1h; Sulphur trioxide is opened vacuum absorption device after fully reacting, sulfur dioxide gas body and function aqueous sodium hydroxide solution that vacuum is pulled out absorb prepare that the pH value is 11～12, mass percent concentration is 90% sodium sulfite solution.Then with sulfonation reaction still internal reaction material be warming up to 145 ℃ the insulation 3h, react to the total acidity of solution be 30%; Be cooled to 125 ℃ then and add water 600ml, insulation 20min, the total acidity that is hydrolyzed into solution is 28%; Be discharged in the condensation pot, controlled temperature to 78 ℃ added formaldehyde solution (specifications and models are 36% a commercial product) 0.40kg and carries out condensation reaction, and formaldehyde solution finishes the sealed reaction pot, 100 ℃ of insulation reaction 5 hours; Insulation finishes to be discharged to the neutralization pot, and using liquid caustic soda to be neutralized to pH value is 7～8 promptly to get aqueous naphthalene water reducer, and liquid product process spraying drying is made the pulvis naphthalene water reducer.
With the above-mentioned mass percent concentration for preparing is that to be prepared into concentration be that 25% sodium sulfite solution 1kg joins in the reactor for 90% sodium sulfite solution; According to the quality of material ratio be: sodium sulfite solution: acetone: formaldehyde solution=1: 0.18: 0.50 in the time of 30 ℃ ± 2 ℃, adds 180g acetone; Stirred 1 hour; Slowly drip formaldehyde solution 500g, the dropping formaldehyde time drips within 3h and finishes, and is warming up to 100 ℃ of insulations and promptly gets aliphatic water reducing agent in 3 hours.
Performance test
The water reducer that embodiment 1～6 is prepared is according to carrying out degree of mobilization, mortar water-reducing rate, compressive strength rate test about the flowing degree of net paste of cement TP among GB8077-87 " concrete admixture uniformity TP " and the GB8076-2008 " concrete admixture ".As relatively, adopted naphthalene series high-efficiency water-reducing agent FDN (note is made FDN), aliphatic high-efficiency water reducing agent product (note is made SAF) commonly used at present to make an experiment simultaneously, the result sees table 1～5.
Table 1 naphthalene water reducer flowing degree of net paste of cement (mm)
Annotate:
(1) 1-1,2-1,3-1,4-1,5-1,6-1 are respectively the naphthalene water reducer that embodiment 1, embodiment 2, embodiment 3, embodiment 4, embodiment 5 and embodiment 6 prepare;
(2) used cement is conch cement 42.5, W/C (wc)=0.29, and admixture dosage is 100 in cement weight, admixture is a pulvis.
Table 2 aliphatic water reducing agent flowing degree of net paste of cement (mm)
Annotate:
(1) 1-2,2-2,3-2,4-2,5-2,6-2 are respectively the aliphatic water reducing agent that embodiment 1, embodiment 2, embodiment 3, embodiment 4, embodiment 5 and embodiment 6 prepare;
(2) used cement is conch cement 42.5, W/C=0.29, and admixture dosage is 100 in cement weight, admixture is an aqua.
Table 3 naphthalene water reducer mortar water-reducing rate (%)
Annotate:
(1) 1-1,2-1,3-1,4-1,5-1,6-1 are respectively the naphthalene water reducer that embodiment 1, embodiment 2, embodiment 3, embodiment 4, embodiment 5 and embodiment 6 prepare;
(2) used cement is: conch cement 42.5, and W/C=0.29, admixture dosage is 100 in cement weight, admixture is a pulvis.
Table 4 aliphatic water reducing agent mortar water-reducing rate (%)
Annotate:
(1) 1-2,2-2,3-2,4-2,5-2,6-2 are respectively embodiment 1, embodiment 2, embodiment 3, embodiment 4, embodiment 5 and 6 synthetic aliphatic water reducing agents of embodiment;
(2) conch cement 42.5, W/C=0.29, and admixture dosage is 100 in cement weight, admixture is an aqua.
The concrete ultimate compression strength of table 5 water reducer
Annotate:
(1) used cement is conch cement 42.5;
(2) 1-1,2-1,3-1,4-1,5-1,6-1 are respectively embodiment 1, embodiment 2, embodiment 3, embodiment 4, embodiment 5 and embodiment 6 synthetic naphthalene water reducers, and FDN is a naphthalene series high-efficiency water-reducing agent, and volume is 0.75%, and admixture is a pulvis;
(3) 1-2,2-2,3-2,4-2,5-2,6-2 are respectively embodiment 1～6 synthetic aliphatic water reducing agent, and SAF is an aliphatic high-efficiency water reducing agent, and volume is 1.5%, and admixture is an aqua;
(4) C represents cement; S represents sand; G represents stone; W represents water; D represents the sky.
Test result by table 1～5 can be known; By the naphthalene series high-efficiency water-reducing agent that obtains of the inventive method preparation and aliphatic high-efficiency water reducing agent under the same test condition each item performance index of each item performance and comparative sample close, and all reached the quality standard of GB8076-2008 defined.
Claims (5)
1. the method for coproduction naphthalene water reducer and aliphatic water reducing agent comprises:
(1) in closed reactor; NAPTHALENE FLAKES. (INDUSTRIAL GRADE is warming up to 120 ~ 160 ℃, and adding mass percent concentration is the vitriol oil more than 95%, feeds sulphur trioxide; Reaction is more than 0.5 hour; Open vacuum unit then,, react that the vitriolic mass percent concentration is 22%～34% to the solution enclosed system insulation reaction 2～4h under 140～170 ℃ of conditions; Through vacuum unit the gas in the reaction system is evacuated in the absorption unit that aqueous sodium hydroxide solution is housed simultaneously, prepares recovery solution;
(2) under 100～160 ℃ of conditions, add entry in the closed reactor in step (1), insulation 10～40min, the vitriolic mass percent concentration is 19%～30% in hydrolysis reaction to the solution then;
(3) reaction mixture that obtains in the step (2) is cooled to 60～95 ℃, adds formaldehyde solution, condensation reaction is 4～8 hours under 100～130 ℃ of conditions;
(4) after condensation reaction was accomplished, the pH value that adding sodium hydroxide is neutralized to reaction mixture was 7～9, obtains naphthalene water reducer through spraying drying;
(5) the recovery solution that obtains in the step (1) is joined in another reaction vessel, under 20～50 ℃ of conditions, add acetone then, stir more than the 0.5h, add formaldehyde solution then, be warming up to 90～105 ℃, react and obtained aliphatic water reducing agent in 2～5 hours;
Used recovery solution is that the pH value is 4 ~ 9 in the described step (5), mass percent concentration is 20～40% S-WAT and the mixed aqueous solution of sodium sulfite anhy 96; The mass ratio of used recovery solution, acetone and formaldehyde solution is 1:0.1～0.4:0.3～0.7 in the described step (5).
2. the method for coproduction naphthalene water reducer according to claim 1 and aliphatic water reducing agent; It is characterized in that the mass ratio of used NAPTHALENE FLAKES. (INDUSTRIAL GRADE and the vitriol oil, sulphur trioxide and formaldehyde solution is 1:0.1～0.9:0.1～0.9:0.4～0.7 in described step (1) and the step (3).
3. the method for coproduction naphthalene water reducer according to claim 1 and aliphatic water reducing agent is characterized in that, the mass ratio of the NAPTHALENE FLAKES. (INDUSTRIAL GRADE that adds in water that adds in the described step (2) and the step (1) is 0.3～0.8:1.
4. according to the method for described coproduction naphthalene water reducer of the arbitrary claim of claim 1 ~ 3 and aliphatic water reducing agent; It is characterized in that; NAPTHALENE FLAKES. (INDUSTRIAL GRADE mixes with washing oil earlier in the described step (1), in the mixture quality percentage composition of NAPTHALENE FLAKES. (INDUSTRIAL GRADE greater than 10% less than 100%.
5. according to the method for described coproduction naphthalene water reducer of the arbitrary claim of claim 1 ~ 3 and aliphatic water reducing agent; It is characterized in that; NAPTHALENE FLAKES. (INDUSTRIAL GRADE mixes with methylnaphthalene earlier in the described step (1), in the mixture quality percentage composition of NAPTHALENE FLAKES. (INDUSTRIAL GRADE greater than 10% less than 100%.
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| CN107573472B (en) * | 2017-08-31 | 2019-10-29 | 浙江吉盛化学建材有限公司 | A kind of production technology of aliphatic water reducing agent |
| CN110482900A (en) * | 2019-08-03 | 2019-11-22 | 徐州巨龙新材料科技有限公司 | A kind of retardation setting type fatty family water-reducing agent and preparation method thereof |
| CN111960712A (en) * | 2020-08-26 | 2020-11-20 | 安徽鑫固环保股份有限公司 | Method for synthesizing water reducing agent by using sulfur trioxide waste gas |
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| CN1355148A (en) * | 2000-11-24 | 2002-06-26 | 周效懿 | Naphthalene-series water-reducing strengthening agent for concrete and its preparing process |
| CN101186459A (en) * | 2007-12-04 | 2008-05-28 | 北京工业大学 | Method for preparing aliphatic high efficiency water reducing agent by using industrial by-product and application thereof |
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| CN101186459A (en) * | 2007-12-04 | 2008-05-28 | 北京工业大学 | Method for preparing aliphatic high efficiency water reducing agent by using industrial by-product and application thereof |
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