CN106632938B - A kind of energy saving preparation method and its special equipment of naphthalene water reducer - Google Patents
A kind of energy saving preparation method and its special equipment of naphthalene water reducer Download PDFInfo
- Publication number
- CN106632938B CN106632938B CN201610836057.4A CN201610836057A CN106632938B CN 106632938 B CN106632938 B CN 106632938B CN 201610836057 A CN201610836057 A CN 201610836057A CN 106632938 B CN106632938 B CN 106632938B
- Authority
- CN
- China
- Prior art keywords
- naphthalene
- water
- kettle
- heat exchange
- passed
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
- C04B24/20—Sulfonated aromatic compounds
- C04B24/22—Condensation or polymerisation products thereof
- C04B24/226—Sulfonated naphtalene-formaldehyde condensation products
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G16/00—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00
- C08G16/02—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00 of aldehydes
- C08G16/0212—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00 of aldehydes with acyclic or carbocyclic organic compounds
- C08G16/0218—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00 of aldehydes with acyclic or carbocyclic organic compounds containing atoms other than carbon and hydrogen
- C08G16/0237—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00 of aldehydes with acyclic or carbocyclic organic compounds containing atoms other than carbon and hydrogen containing sulfur
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses the energy saving preparation methods and its special equipment of a kind of naphthalene water reducer.The energy saving preparation method of naphthalene water reducer of the present invention includes (1) sulfonation: naphthalene being put into sulphonation kettle, heating steam is passed through into heat exchange jacket, naphthalene is heated, the concentrated sulfuric acid is added, continues logical heating steam, obtains sulfonation material；(2) cooling dilution: sulfonation material obtained by step (1) is transferred to condensation kettle, so that material is cooled down, and room temperature dilution water is added；(3) it is condensed: super acids and formalin, the water heating and thermal insulation being passed through in tank into heat exchange jacket is added；(4) it neutralizes: condensation material obtained by step (3) being transferred to neutralization kettle, sodium hydroxide solution is added, neutralization reactant obtains the naphthalene water reducer.The performance for the naphthalene water reducer that energy conservation preparation method of the present invention is synthesized with using conventional method is suitable；The production energy consumption of naphthalene water reducer can be effectively reduced simultaneously, to reduce the production cost of product, promote the cost performance of product.
Description
Technical field
The invention belongs to the field of building materials, are related to a kind of preparation method of chemical admixture, and in particular to a kind of naphthalene system
The energy saving preparation method and its special equipment of water-reducing agent.
Background technique
Cement water reducing agent can obviously reduce the water being added when mixing and stirring concrete, while it is new to increase substantially concrete
The intensity after mobile performance and hardening when mixing, to improve the quality of engineering.Naphthalene water reducer therein have diminishing it is high, with
The features such as adaptability of different cement is good, good, moderate with additive compound performance is still that domestic production amount is maximum, makes at present
With most wide water-reducing agent.
The preparation method of conventional naphthalene water reducer mainly includes sulfonation, hydrolysis, condensation, neutralization.In sulfonation procedure
In, make the mixture of liquid naphthalene and sulfuric acid in 160~170 DEG C of heat preservation sulfonation a few hours by heating steam；It then will with cooling water
Reactant is cooled to 110~120 DEG C, and hydrolysis water is added and continues (to need using heating for heat preservation 0.5~1 hour at this temperature
Steam maintenance system temperature)；System is cooled to 90~95 DEG C with cooling water again, instill formalin and is kept the temperature at about 100 DEG C
Condensation a few hours (are also required to using heating steam maintenance system temperature)；Finally under conditions of persistently cooling, slowly add
Enter liquid alkaline and reactant is neutralized to neutral naphthalene water reducer finished product to obtain the final product.Need multiple heating and cooling anti-in the whole process
System is answered, needs a large amount of steam consumption in heating and insulating process, and consumes a large amount of cooling water in temperature-fall period,
The energy consumption of entire production process is very big.
The research of current naphthalene water reducer mostly concentrates on performance improvement, the reduction cost of raw material, cleanly production etc.
Aspect, the report in terms of naphthalene water reducer production energy-saving is very few in the prior art.Application No. is
201010259902 Chinese patent literature discloses " method of polycyclic aromatic hydrocarbon (PAH) water reducer energy-saving drying ", by polycyclic virtue
The neutralization stage of hydrocarbon water-reducing agent (such as naphthalene water reducer) replaces liquid base to be neutralized using solid base, improves water-reducing agent mother
The solid content of liquid, so that the energy consumption that water-reducing agent is dried into pulvis is reduced, but this method is not in water-reducing agent preparation process
Energy consumption reduce measure, it is energy-saving essentially without going to realize in terms of production technology and equipment technology.
It with the propulsion of China's industrialization progress, will increasingly pay attention to the energy-saving of production technology, therefore develop naphthalene system
The energy saving preparation method of water-reducing agent also will be and promote the improved important directions of naphthalene water reducer industrialization.
Summary of the invention
For the problem that energy consumption in existing naphthalene water reducer production process is larger, the present invention is set from synthesis technology and production
Standby two aspect is started with together, provides a kind of energy saving preparation method of naphthalene water reducer.
Those skilled in the art's discovery, in the condensation step for preparing naphthalene water reducer, is added a certain amount of super acids,
It can obviously reduce the condensation temp of reaction, and keep final prepared naphthalene water reducer end properties unaffected.
Those skilled in the art also found, introduce in the condensation step for preparing naphthalene water reducer of the present invention super
The performance of strong acid, the hydrolysis incubation step before can saving, gained water-reducing agent product is basically unchanged.
A kind of energy saving preparation method of naphthalene water reducer of the present invention, includes the following steps:
(1) sulfonation: putting into sulphonation kettle for naphthalene, and 165 ± 2 DEG C of heating steam is passed through into heat exchange jacket, naphthalene is heated molten
Change to 130 DEG C~150 DEG C, the concentrated sulfuric acid that concentration is 98%~100% is added, continues logical heating steam, make reactant at 160 DEG C
~170 DEG C of heat preservations obtain sulfonation material in 1.5~4 hours；
(2) cooling dilution: sulfonation material obtained by step (1) is transferred to condensation kettle, tank is passed through into heat exchange jacket
In water it is cooling, so that material is cooled to 100 DEG C~105 DEG C, then pass to external room temperature cooling water, make material be cooled to 80 DEG C~
85 DEG C, the room temperature dilution water of the sulfonation material gross mass 5%~20% is added, temperature of charge is down to 75 DEG C~80 DEG C；
(3) it is condensed: super acids is added, 37% formalin are then added, the water being passed through in tank into heat exchange jacket
Heating and thermal insulation is condensed material 4~6 hours at 80 ± 3 DEG C；
(4) it neutralizes: condensation material obtained by step (3) is transferred to neutralization kettle, closing neutralization all blow valves of kettle makes system
Closed, the sodium hydroxide solution of addition 30%~35% is passed through when system temperature rises to 105 DEG C or more into heat exchange jacket
Water cooling in tank, makes system temperature be no more than 120 DEG C, and reactant is neutralized to after pH value is 6~8 and stops adding hydroxide
Sodium solution, continuing to be passed through the water in tank makes product be cooled to 100 DEG C~105 DEG C, then is passed through external room temperature cooling water, makes object
Material is cooled to 90 DEG C hereinafter, the naphthalene water reducer product that can discharge to obtain；
The naphthalene refers to the crude naphthalene of refined naphthalene or effective content >=95%；The molar ratio of the concentrated sulfuric acid and naphthalene be (1.3~
1.6): 1；
The super acids and the molar ratio of naphthalene are (0.1~0.5): 1；The molar ratio of the formaldehyde and naphthalene be (1.0~
1.2): 1；The dosage of super acids is too high or too low all to be had some impact on the water-reducing property of final products.
In above-mentioned steps (2) and (4), the temperature for the water in the tank for cooling being passed through is at 95 DEG C or less；It is above-mentioned
In step (3), the temperature for the water in the tank for heating and thermal insulation being passed through is at 85 DEG C or more.
The super acids are perchloric acid, trifluoromethanesulfonic acid, any several combinations with arbitrary proportion in fluosulfonic acid.
The special equipment for implementing a kind of energy saving preparation method of naphthalene water reducer of the present invention, specifically include that sulphonation kettle,
Condensation kettle neutralizes kettle, tank, pump, the control valve and pipeline for connecting each equipment；
Stirring motor is equipped with above the sulphonation kettle, condensation kettle and neutralization kettle, inside is equipped with blender, external to be equipped with heat exchange
Collet；
Water in the tank is gone out by pumping, through different pipeline and control valve, inputs condensation kettle or neutralization by lower end
Then the heat exchange jacket of kettle is exported by heat exchange jacket upper end, using different pipeline and control valve, flow back to former tank or its
His tank；
The sulphonation kettle inputs heating steam by heat exchange jacket upper end, then is exported by heat exchange jacket lower end.
It the condensation kettle and neutralizes kettle and room temperature cooling water can also be inputted by heat exchange jacket lower end, then from heat exchange jacket upper end
It exports to the Water Treatment in Circulating Cooling System of plant area.
The tank quantity is at least three, according to heat exchange situation and tank needed for naphthalene water reducer preparation process
The temperature of middle water for exchanging heat in turn to reaction kettle.
The method that energy conservation preparation method of the present invention uses residual heat recovery, using the water in the tank as medium,
Partial heat caused by the cooling of sulfonation material and neutralization procedure is brought into condensation step and is used to heating and thermal insulation, it is completely left out
Heating energy consumption needed for condensation step, and greatly reduce the cooling-water consumption of sulfonation material cooling and neutralization procedure.In addition,
Heating energy consumption can also be saved to a certain extent by saving hydrolysis heat preservation process.
The naphthalene system diminishing synthesized using the performance of the naphthalene water reducer of the method for the invention preparation with using conventional method
The performance of agent is suitable.
The production energy consumption of naphthalene water reducer can be effectively reduced in energy conservation preparation method of the present invention, to reduce product
Production cost, promote the cost performance of product.
Detailed description of the invention
Fig. 1 is the equipment and flow diagram of naphthalene water reducer energy conservation preparation method of the present invention.
In figure, 1- sulphonation kettle, 2- condensation kettle, in 3- and kettle, 4- stirring motor, 5- blender, 6- heat exchange jacket,
7- control valve, 8- heating or cooling medium feed-line, 9- pump, 10- tank, A- heat steam input, B- heating
Steam output, the input of C- room temperature cooling water, the output of D- room temperature cooling water.
Specific embodiment
The contents of the present invention are made into one below in conjunction with Figure of description for the ease of the understanding of those skilled in the art
Walk explanation.Certainly the invention is not limited to the specific embodiment, general replacement known to those skilled in the art
It is included within the scope of protection of the present invention.Secondly, the present invention has carried out detailed statement using schematic diagram, it is real the present invention is described in detail
When example, for ease of description, schematic diagram is not partially enlarged in proportion to the general scale, should not be in this, as limitation of the invention.
Naphthalene, sulfuric acid, super acids, formalin and sodium hydroxide solution used in comparative example and embodiment of the present invention be
General technical grade product.
In order to realize energy saving preparation method of the present invention, using production equipment and process as shown in the figure.It is involved
Production equipment specifically include that sulphonation kettle 1, condensation kettle 2, neutralize kettle 3, tank 10, pump 9, each equipment of connection 7 and of control valve
Pipeline 8 and the attached stirring motor 4 of reaction kettle, blender 5, heat exchange jacket 6.Water in the tank 10 is taken out by pump 9
Out, through different pipeline and control valve, condensation kettle 2 is inputted by lower end or neutralizes the heat exchange jacket of kettle 3, then by heat exchange jacket
End output, using different pipeline and control valve, flows back to former tank or other tanks.The condensation kettle 2 and neutralization kettle 3
Room temperature cooling water can also be inputted by heat exchange jacket lower end, then exported from heat exchange jacket upper end to the circulating water cooling treatment of plant area
System.The sulphonation kettle 1 inputs heating steam by heat exchange jacket upper end, then is exported by heat exchange jacket lower end.
There are three the tanks, according to water in heat exchange situation needed for naphthalene water reducer preparation process and tank 10
Temperature is used to exchange heat in turn to condensation kettle 2 or neutralization kettle 3.
Embodiment 1
Using production equipment and process as shown in the figure, using the water in the tank as medium, sulfonation material is cooled down
It brings with partial heat caused by neutralization procedure into condensation step and is used to heating and thermal insulation, super acids are added simultaneously in condensation step
And save hydrolysis heat preservation process, comprising the following steps:
(1) sulfonation: 95% naphthalene 1617kg (12kmol) is put into sulphonation kettle, 165 ± 2 DEG C are passed through into heat exchange jacket
Steam is heated, naphthalene heating is melted to 140 DEG C, the concentrated sulfuric acid 1800kg (18kmol) that concentration is 98% is added, continues logical heating
Steam makes reactant keep the temperature 2.5 hours at 165 ± 3 DEG C and obtains sulfonation material；
(2) cooling dilution: sulfonation material obtained by step (1) is transferred to condensation kettle, tank is passed through into heat exchange jacket
In water it is cooling, so that material is cooled to 100 DEG C, then pass to external room temperature cooling water, material is made to be cooled to 80 DEG C, be added
500kg room temperature dilution water, temperature of charge are down to 76 DEG C；
(3) it is condensed: 70% perchloric acid 287kg (2kmol) is added, 37% formalin 973kg is then added
(12kmol), the water heating and thermal insulation being passed through in tank into heat exchange jacket are condensed material 5 hours at 80 ± 3 DEG C；
(4) it neutralizes: condensation material obtained by step (3) is transferred to neutralization kettle, closing neutralization all blow valves of kettle makes system
It is closed, 32% sodium hydroxide solution is added, when system temperature rises to 105 DEG C or more, tank is passed through into heat exchange jacket
In water cooling, make system temperature be no more than 120 DEG C, by reactant be neutralized to pH value be 7~8 after stop adding sodium hydroxide it is molten
Liquid, continuing to be passed through the water in tank makes product be cooled to 105 DEG C, then is passed through external room temperature cooling water, and material is made to be cooled to 90
DEG C hereinafter, the product that can discharge to obtain.
Embodiment 2
Using production equipment and process similar to Example 1, comprising the following steps:
(1) sulfonation: 98% naphthalene 1567kg (12kmol) is put into sulphonation kettle, 165 ± 2 DEG C are passed through into heat exchange jacket
Steam is heated, naphthalene heating is melted to 145 DEG C, the concentrated sulfuric acid 1584kg (16kmol) that concentration is 99% is added, continues logical heating
Steam makes reactant keep the temperature 4 hours at 165 ± 3 DEG C and obtains sulfonation material；
(2) cooling dilution: sulfonation material obtained by step (1) is transferred to condensation kettle, tank is passed through into heat exchange jacket
In water it is cooling, so that material is cooled to 102 DEG C, then pass to external room temperature cooling water, material is made to be cooled to 82 DEG C, be added
300kg room temperature dilution water, temperature of charge are down to 78 DEG C；
(3) it is condensed: 98% trifluoromethanesulfonic acid 765kg (5kmol) is added, 37% formalin 1135kg is then added
(14kmol), the water heating and thermal insulation being passed through in tank into heat exchange jacket are condensed material 4.5 hours at 80 ± 3 DEG C；
(4) it neutralizes: condensation material obtained by step (3) is transferred to neutralization kettle, closing neutralization all blow valves of kettle makes system
It is closed, 32% sodium hydroxide solution is added, when system temperature rises to 105 DEG C or more, tank is passed through into heat exchange jacket
In water cooling, make system temperature be no more than 120 DEG C, by reactant be neutralized to pH value be 7~8 after stop adding sodium hydroxide it is molten
Liquid, continuing to be passed through the water in tank makes product be cooled to 100 DEG C, then is passed through external room temperature cooling water, and material is made to be cooled to 90
DEG C hereinafter, the product that can discharge to obtain.
Embodiment 3
Using production equipment and process similar to Example 1, comprising the following steps:
(1) sulfonation: 98% naphthalene 1567kg (12kmol) is put into sulphonation kettle, 165 ± 2 DEG C are passed through into heat exchange jacket
Steam is heated, naphthalene heating is melted to 145 DEG C, the concentrated sulfuric acid 1683kg (17kmol) that concentration is 99% is added, continues logical heating
Steam makes reactant keep the temperature 3.5 hours at 165 ± 3 DEG C and obtains sulfonation material；
(2) cooling dilution: sulfonation material obtained by step (1) is transferred to condensation kettle, tank is passed through into heat exchange jacket
In water it is cooling, so that material is cooled to 102 DEG C, then pass to external room temperature cooling water, material is made to be cooled to 82 DEG C, be added
320kg room temperature dilution water, temperature of charge are down to 78 DEG C；
(3) it is condensed: 97% fluosulfonic acid 186kg (1.8kmol) is added, 37% formalin 1135kg is then added
(14kmol), the water heating and thermal insulation being passed through in tank into heat exchange jacket are condensed material 4.5 hours at 80 ± 3 DEG C；
(4) it neutralizes: condensation material obtained by step (3) is transferred to neutralization kettle, closing neutralization all blow valves of kettle makes system
It is closed, 32% sodium hydroxide solution is added, when system temperature rises to 105 DEG C or more, tank is passed through into heat exchange jacket
In water cooling, make system temperature be no more than 120 DEG C, by reactant be neutralized to pH value be 7~8 after stop adding sodium hydroxide it is molten
Liquid, continuing to be passed through the water in tank makes product be cooled to 100 DEG C, then is passed through external room temperature cooling water, and material is made to be cooled to 90
DEG C hereinafter, the product that can discharge to obtain.
Embodiment 4
Using production equipment and process similar to Example 1, comprising the following steps:
(1) sulfonation: 97% naphthalene 1584kg (12kmol) is put into sulphonation kettle, 165 ± 2 DEG C are passed through into heat exchange jacket
Steam is heated, naphthalene heating is melted to 135 DEG C, the concentrated sulfuric acid 1881kg (19kmol) that concentration is 99% is added, continues logical heating
Steam makes reactant keep the temperature 1.5 hours at 165 ± 3 DEG C and obtains sulfonation material；
(2) cooling dilution: sulfonation material obtained by step (1) is transferred to condensation kettle, tank is passed through into heat exchange jacket
In water it is cooling, so that material is cooled to 105 DEG C, then pass to external room temperature cooling water, material is made to be cooled to 85 DEG C, be added
650kg room temperature dilution water, temperature of charge are down to 77 DEG C；
(3) it is condensed: the trifluoromethanesulfonic acid 153kg (1kmol) of 70% perchloric acid 144kg (1kmol) and 98% is added, so
After 37% formalin 973kg (12kmol) is added, the water heating and thermal insulation being passed through in tank into heat exchange jacket makes material exist
80 ± 3 DEG C are condensed 6 hours；
(4) it neutralizes: condensation material obtained by step (3) is transferred to neutralization kettle, closing neutralization all blow valves of kettle makes system
It is closed, 32% sodium hydroxide solution is added, when system temperature rises to 105 DEG C or more, tank is passed through into heat exchange jacket
In water cooling, make system temperature be no more than 120 DEG C, by reactant be neutralized to pH value be 7~8 after stop adding sodium hydroxide it is molten
Liquid, continuing to be passed through the water in tank makes product be cooled to 102 DEG C, then is passed through external room temperature cooling water, and material is made to be cooled to 90
DEG C hereinafter, the product that can discharge to obtain.
Embodiment 5
Using production equipment and process similar to Example 1, comprising the following steps:
(1) sulfonation: 95% naphthalene 1617kg (12kmol) is put into sulphonation kettle, 165 ± 2 DEG C are passed through into heat exchange jacket
Steam is heated, naphthalene heating is melted to 135 DEG C, the concentrated sulfuric acid 1800kg (18kmol) that concentration is 98% is added, continues logical heating
Steam makes reactant keep the temperature 3.5 hours at 165 ± 3 DEG C and obtains sulfonation material；
(2) cooling dilution: sulfonation material obtained by step (1) is transferred to condensation kettle, tank is passed through into heat exchange jacket
In water it is cooling, so that material is cooled to 100 DEG C, then pass to external room temperature cooling water, material is made to be cooled to 80 DEG C, be added
500kg room temperature dilution water, temperature of charge are down to 78 DEG C；
(3) it is condensed: 70% perchloric acid 144kg (1kmol) is added, 37% formalin 1054kg is then added
(13kmol), the water heating and thermal insulation being passed through in tank into heat exchange jacket are condensed material 5 hours at 80 ± 3 DEG C；
(4) it neutralizes: condensation material obtained by step (3) is transferred to neutralization kettle, closing neutralization all blow valves of kettle makes system
It is closed, 32% sodium hydroxide solution is added, when system temperature rises to 105 DEG C or more, tank is passed through into heat exchange jacket
In water cooling, make system temperature be no more than 120 DEG C, by reactant be neutralized to pH value be 7~8 after stop adding sodium hydroxide it is molten
Liquid, continuing to be passed through the water in tank makes product be cooled to 105 DEG C, then is passed through external room temperature cooling water, and material is made to be cooled to 90
DEG C hereinafter, the product that can discharge to obtain.
Embodiment 6
Using production equipment and process similar to Example 1, comprising the following steps:
(1) sulfonation: 95% naphthalene 1617kg (12kmol) is put into sulphonation kettle, 165 ± 2 DEG C are passed through into heat exchange jacket
Steam is heated, naphthalene heating is melted to 145 DEG C, the concentrated sulfuric acid 1800kg (18kmol) that concentration is 98% is added, continues logical heating
Steam makes reactant keep the temperature 2 hours at 165 ± 3 DEG C and obtains sulfonation material；
(2) cooling dilution: sulfonation material obtained by step (1) is transferred to condensation kettle, tank is passed through into heat exchange jacket
In water it is cooling, so that material is cooled to 100 DEG C, then pass to external room temperature cooling water, material is made to be cooled to 80 DEG C, be added
550kg room temperature dilution water, temperature of charge are down to 75 DEG C；
(3) it is condensed: 70% perchloric acid 933kg (6.5kmol) is added, 37% formalin 1054kg is then added
(13kmol), the water heating and thermal insulation being passed through in tank into heat exchange jacket are condensed material 5 hours at 80 ± 3 DEG C；
(4) it neutralizes: condensation material obtained by step (3) is transferred to neutralization kettle, closing neutralization all blow valves of kettle makes system
It is closed, 32% sodium hydroxide solution is added, when system temperature rises to 105 DEG C or more, tank is passed through into heat exchange jacket
In water cooling, make system temperature be no more than 120 DEG C, by reactant be neutralized to pH value be 7~8 after stop adding sodium hydroxide it is molten
Liquid, continuing to be passed through the water in tank makes product be cooled to 105 DEG C, then is passed through external room temperature cooling water, and material is made to be cooled to 90
DEG C hereinafter, the product that can discharge to obtain.
Comparative example 1
A kind of synthetic method of routine naphthalene water reducer, cools down only with conventional steam heating and room temperature cooling water,
Super acids are not added in condensation step and still include common hydrolysing step, comprising the following steps:
(1) sulfonation: 95% naphthalene 1617kg (12kmol) is put into sulphonation kettle, 165 ± 2 DEG C are passed through into heat exchange jacket
Steam is heated, naphthalene heating is melted to 140 DEG C, the concentrated sulfuric acid 1800kg (18kmol) that concentration is 98% is added, continues logical heating
Steam makes reactant keep the temperature 2.5 hours at 165 ± 3 DEG C and obtains sulfonation material；
(2) it hydrolyzes: sulfonation material obtained by step (1) being transferred to condensation kettle, room temperature cooling water is passed through into heat exchange jacket
It is cooling, so that material is cooled to 120 DEG C, 500kg ordinary-temp hydrolysis water is added, heating steam is passed through into heat exchange jacket, makes reactant
1 hour is kept the temperature in 115 ± 5 DEG C of hydrolysis, room temperature cooling water is then passed to, material is made to be cooled to 95 DEG C；
(3) it is condensed: and then 37% formalin 973kg (12kmol) is added, it is passed through heating steam into heat exchange jacket, makes
Material 100 ± 3 DEG C progress condensation reaction 5.5 hours；
(4) it neutralizes: condensation material obtained by step (3) being transferred to neutralization kettle, room temperature cooling water is passed through into heat exchange jacket
It is cooling, when system temperature is down to 90 DEG C or less, 32% sodium hydroxide solution is added, control feed rate surpasses system temperature not
95 DEG C are crossed, reactant is neutralized to after pH value is 7~8 and stops adding sodium hydroxide solution, continues to be passed through room temperature cooling water, makes material
90 DEG C are cooled to hereinafter, the product that can discharge to obtain.
Comparative example 2
In addition to the condensation temp in step (3) is changed to 80 ± 3 DEG C, other synthesis technologic parameters are identical as comparative example 1.
Performance comparison
The performance of prepared naphthalene water reducer is investigated by concrete test.Wherein cement used is the field Jiangnan little Ye
52.5 cement of PII, flyash are II grades of flyash, and sand is the middle sand of fineness modulus 2.7, and coarse aggregate is the continuous grade of 5~20mm
With rubble.Concrete mix: cement 260kg/m3, flyash 110kg/m3, sand 770kg/m3, rubble 1080kg/m3, water
160kg/m3.Water-reducing agent volume is calculated as 0.5% on the basis of cement quality, by the solid amount of folding.Test is provided according to GB8076-2008
Condition and method carry out test and determination data, test result it is as follows.
1 embodiment concrete test data comparison of table
It can be seen that (1) in condensation step prepared by naphthalene water reducer from the above concrete test correlation data to be added
The constant water-reducing agent of performance can be made in super acids at a lower temperature, and condensation temp is reduced when without super acids can seriously affect very
To the water-reducing property for losing product；(2) it mixes the concrete strength of naphthalene water reducer prepared by the method for the present invention and is added and use
The concrete strength of the naphthalene water reducer of conventional method preparation does not have difference, construction quality will not be brought to ask in engineer application
Topic；(3) dosage of super acids is too high or too low in condensation step can all have some impact on the water-reducing property of final products.
Energy consumption comparison
The energy saving preparation method of naphthalene water reducer of the present invention, by needed for the completely left out condensation step of residual heat recovery
Heating steam consumption, also by remove hydrolysing step eliminate hydrolysis heat preservation process needed for heating steam consumption, additionally
Greatly reduce the cooling-water consumption of sulfonation material cooling and neutralization procedure.Only from steam consumption, this compares on one side below
The energy consumption of more different preparation methods.Each embodiment technique carries out the continuous production of 50 kettles, calculates every t naphthalene water reducer
The steam consumption of product (folding is solid), the results are shown in Table 2.
The energy consumption comparison of 2 different process of table
By comparing the steam consumption number of comparative example 1 and embodiment 1,2,3,4 it has been found that preparation method of the present invention by
It does not need additionally to consume heating steam in hydrolysis and condensation step, the steam mono-consumption about 30~50% of product can be reduced.Except this
In addition, the method for the present invention can also effectively reduce the consumption of cooling water.Therefore, preparation method of the present invention has significant section
The effect that can be lowered consumption.
Claims (5)
1. a kind of energy saving preparation method of naphthalene water reducer, which is characterized in that specifically comprise the following steps:
(1) sulfonation: putting into sulphonation kettle for naphthalene, and 165 ± 2 DEG C of heating steam is passed through into heat exchange jacket, and naphthalene heating is melted to
130 DEG C~150 DEG C, the concentrated sulfuric acid that concentration is 98%~100% is added, continues logical heating steam, make reactant 160 DEG C~
170 DEG C of heat preservations obtain sulfonation material in 1.5~4 hours；
(2) cooling dilution: sulfonation material obtained by step (1) is transferred to condensation kettle, is passed through in tank into heat exchange jacket
Water is cooling, so that material is cooled to 100 DEG C~105 DEG C, then passes to external room temperature cooling water, material is made to be cooled to 80 DEG C~85
DEG C, the room temperature dilution water of the sulfonation material gross mass 5%~20% is added, temperature of charge is down to 75 DEG C~80 DEG C；
(3) it is condensed: super acids is added, 37% formalin is then added, the water heating being passed through into heat exchange jacket in tank
Heat preservation is condensed material 4~6 hours at 80 ± 3 DEG C；
(4) it neutralizes: condensation material obtained by step (3) is transferred to neutralization kettle, closing neutralization all blow valves of kettle keeps system closed,
The sodium hydroxide solution for being added 30%~35% is passed through tank into heat exchange jacket when system temperature rises to 105 DEG C or more
In water cooling, make system temperature be no more than 120 DEG C, by reactant be neutralized to pH value be 6~8 after stop adding sodium hydroxide it is molten
Liquid, continuing to be passed through the water in tank makes product be cooled to 100 DEG C~105 DEG C, then is passed through external room temperature cooling water, drops material
Temperature is to 90 DEG C hereinafter, the naphthalene water reducer that can discharge to obtain；
The naphthalene refers to the crude naphthalene of refined naphthalene or effective content >=95%；The molar ratio of the concentrated sulfuric acid and naphthalene be (1.3~
1.6): 1；
The super acids and the molar ratio of naphthalene are (0.1~0.5): 1；The molar ratio of the formaldehyde and naphthalene is (1.0~1.2): 1；
The special equipment for implementing the energy saving preparation method of naphthalene water reducer mainly includes sulphonation kettle (1), condensation kettle (2), neutralizes kettle
(3), tank (10), pump (9), the control valve 7 for connecting each equipment) and pipeline (8)；The sulphonation kettle (1), condensation kettle (2) and
It neutralizes and is equipped with stirring motor (4) above kettle (3), inside is equipped with blender (5), and outside is equipped with heat exchange jacket (6)；
Water in the tank is gone out by pumping, through different pipeline and control valve, is inputted condensation kettle by lower end or is neutralized kettle
Then heat exchange jacket is exported by heat exchange jacket upper end, using different pipeline and control valve, flow back to former tank or other storages
Pond；
The sulphonation kettle inputs heating steam by heat exchange jacket upper end, then is exported by heat exchange jacket lower end.
2. a kind of energy saving preparation method of naphthalene water reducer according to claim 1, which is characterized in that the step (2)
(4) in, the temperature for the water in the tank for cooling being passed through is at 95 DEG C or less；In the step (3), what is be passed through is used for
The temperature of water in the tank of heating and thermal insulation is at 85 DEG C or more.
3. a kind of energy saving preparation method of naphthalene water reducer according to claim 2, which is characterized in that the super acids are
Perchloric acid, trifluoromethanesulfonic acid, any several combinations with arbitrary proportion in fluosulfonic acid.
4. a kind of energy saving preparation method of naphthalene water reducer according to claim 3, which is characterized in that the condensation kettle and
It neutralizes kettle and room temperature cooling water is inputted by heat exchange jacket lower end, then export from heat exchange jacket upper end to the circulating water cooling treatment of plant area
System.
5. a kind of energy saving preparation method of naphthalene water reducer according to claim 4, which is characterized in that the tank number
Amount is at least three.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610836057.4A CN106632938B (en) | 2016-09-20 | 2016-09-20 | A kind of energy saving preparation method and its special equipment of naphthalene water reducer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610836057.4A CN106632938B (en) | 2016-09-20 | 2016-09-20 | A kind of energy saving preparation method and its special equipment of naphthalene water reducer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106632938A CN106632938A (en) | 2017-05-10 |
| CN106632938B true CN106632938B (en) | 2019-01-01 |
Family
ID=58852106
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610836057.4A Active CN106632938B (en) | 2016-09-20 | 2016-09-20 | A kind of energy saving preparation method and its special equipment of naphthalene water reducer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106632938B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111790305A (en) * | 2020-07-17 | 2020-10-20 | 海娇 | Processing device of water reducing agent |
| CN113087867A (en) * | 2021-04-12 | 2021-07-09 | 罗小泉 | Water reducing agent and preparation method thereof |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101054273A (en) * | 2006-12-06 | 2007-10-17 | 攀钢集团钢城企业总公司 | Method of producing naphthalene series water reducing agent by refined naphthalene residual oil fraction |
| CN101580352A (en) * | 2009-03-19 | 2009-11-18 | 四川吉龙化学建材有限公司 | Naphthalene water-reducing agent and processing technique of homologous dispersant thereof |
| CN101585675A (en) * | 2009-06-22 | 2009-11-25 | 江苏特密斯混凝土外加剂有限公司 | Sulphonation method for naphthalene series water reducing agent without naphthalene discharging |
| CN101844891A (en) * | 2010-04-13 | 2010-09-29 | 宫振鑫 | Novel process for producing naphthalene water reducer of concrete admixture |
| CN102464464A (en) * | 2010-11-09 | 2012-05-23 | 浙江龙盛集团股份有限公司 | Preparation method of naphthalene series water reducer |
| CN102746195A (en) * | 2011-04-27 | 2012-10-24 | 江苏尼高科技有限公司 | Method for improving sulfonation process of naphthalene-based water reducer |
| CN202988996U (en) * | 2012-09-26 | 2013-06-12 | 山东英泰建材科技有限公司 | Naphthalene-based water reducer compounding production line |
| CN103159424A (en) * | 2013-03-21 | 2013-06-19 | 安徽淮河化工股份有限公司 | Method for producing naphthalene water reducer |
| CN103382092A (en) * | 2013-06-17 | 2013-11-06 | 江苏博特新材料有限公司 | Method for preparing naphthalene series water reducer |
| CN103864332A (en) * | 2014-02-26 | 2014-06-18 | 科之杰新材料集团有限公司 | Preparation method of slump loss resistant naphthalene water reducer |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100453491C (en) * | 2007-05-25 | 2009-01-21 | 河北久强建材有限公司 | Preparation method of naphthalene series dehydragent and special equipment thereof |
| CN201660566U (en) * | 2010-04-13 | 2010-12-01 | 宫振鑫 | Production line equipment of naphthalene sulfonate water-reducing admixture |
| CN203079853U (en) * | 2013-02-26 | 2013-07-24 | 潍坊融荣建材有限公司 | Naphthalene water reducer producing device |
-
2016
- 2016-09-20 CN CN201610836057.4A patent/CN106632938B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101054273A (en) * | 2006-12-06 | 2007-10-17 | 攀钢集团钢城企业总公司 | Method of producing naphthalene series water reducing agent by refined naphthalene residual oil fraction |
| CN101580352A (en) * | 2009-03-19 | 2009-11-18 | 四川吉龙化学建材有限公司 | Naphthalene water-reducing agent and processing technique of homologous dispersant thereof |
| CN101585675A (en) * | 2009-06-22 | 2009-11-25 | 江苏特密斯混凝土外加剂有限公司 | Sulphonation method for naphthalene series water reducing agent without naphthalene discharging |
| CN101844891A (en) * | 2010-04-13 | 2010-09-29 | 宫振鑫 | Novel process for producing naphthalene water reducer of concrete admixture |
| CN102464464A (en) * | 2010-11-09 | 2012-05-23 | 浙江龙盛集团股份有限公司 | Preparation method of naphthalene series water reducer |
| CN102746195A (en) * | 2011-04-27 | 2012-10-24 | 江苏尼高科技有限公司 | Method for improving sulfonation process of naphthalene-based water reducer |
| CN202988996U (en) * | 2012-09-26 | 2013-06-12 | 山东英泰建材科技有限公司 | Naphthalene-based water reducer compounding production line |
| CN103159424A (en) * | 2013-03-21 | 2013-06-19 | 安徽淮河化工股份有限公司 | Method for producing naphthalene water reducer |
| CN103382092A (en) * | 2013-06-17 | 2013-11-06 | 江苏博特新材料有限公司 | Method for preparing naphthalene series water reducer |
| CN103864332A (en) * | 2014-02-26 | 2014-06-18 | 科之杰新材料集团有限公司 | Preparation method of slump loss resistant naphthalene water reducer |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106632938A (en) | 2017-05-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105236798B (en) | A kind of preparation method of naphthalene water reducer | |
| CN106117482B (en) | A kind of modified high-thin arch dam naphthalene water reducer and preparation method thereof | |
| CN101698581B (en) | Foaming agent of waterproof foam concrete, and preparation method | |
| CN106632938B (en) | A kind of energy saving preparation method and its special equipment of naphthalene water reducer | |
| CN106517849A (en) | Oxidation-sulfonation starch water reducing agent preparation method | |
| CN102532045A (en) | Method for producing cyanuric acid from urea used as raw material | |
| CN105801786A (en) | Low-cost modified naphthalene-based superplasticizer with high slump-keeping property and preparation method thereof | |
| CN102060461A (en) | Cement composite grinding aid and preparation method thereof | |
| CN106810412B (en) | Method for improving sulfonation reaction efficiency and production method of dispersing agent MF | |
| CN102372456B (en) | Method for preparing naphthalene series additive from low-acidity process waste water | |
| CN104478285B (en) | A kind of it is applied to the activation reinforcing agent of cement concrete, purposes and preparation method thereof | |
| CN103496871B (en) | A kind of eco-friendly low cost sulfamate high-effective water-reducing agent preparation method | |
| CN109279834A (en) | A kind of shock resistance waterproof foamed cement and preparation method thereof | |
| CN108484852A (en) | A kind of modified naphthalene series water-reducing agent of useless residue in the production process containing phenols | |
| CN105985047A (en) | Modified polycarboxylate water reducer capable of improving strength of concrete | |
| CN106542752B (en) | A kind of poly- cement material of soil and preparation method thereof | |
| CN104628605B (en) | A kind of naphthalene continuous catalysis method of sulfonating and device thereof | |
| CN107986701A (en) | A kind of light heat insulation blocks based on discarded red brick powder and preparation method thereof | |
| CN111004362B (en) | Preparation method of naphthalene-based superplasticizer | |
| CN107778428B (en) | A kind of aliphatic high-efficiency water reducing agent and preparation method thereof | |
| CN102452806A (en) | Novel melamine water reducer and preparation method | |
| CN102399069A (en) | Modified efficient aliphatic water reducing agent and preparation method thereof | |
| CN107601951A (en) | A kind of concrete special starch syrup and preparation method thereof | |
| CN111470793B (en) | High-dispersity high-quality naphthalene-based high-efficiency water reducing agent and preparation method thereof | |
| CN109534712B (en) | Light yellow naphthalene water reducing agent and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |