阅读说明：本技术 一种环保型萘系减水剂的制备方法 (Preparation method of environment-friendly naphthalene water reducer ) 是由 马丽涛 董翠平 王冰 彭城 宋宝 杨道顺 尤健健 于 2020-06-15 设计创作，主要内容包括：本发明涉及到建筑材料技术领域,具体涉及到一种环保型萘系减水剂的制备方法。一种环保型萘系减水剂的制备方法,包括以下步骤：蒸馏残渣预处理、磺化、缩合、中和,本发明采用C3～C6的烷基硅烷偶联剂对蒸馏残渣进行预处理,掺入萘油中作含萘原料制得的萘系减水剂,不仅具有较低的泌水率,且具有较高的减水率和保塑性能。该制备方法操作简单、反应条件易控制,且以蒸馏残渣作原料,不仅降低了萘系减水剂的生产成本,且减少了环境污染。(The invention relates to the technical field of building materials, in particular to a preparation method of an environment-friendly naphthalene water reducer. A preparation method of an environment-friendly naphthalene water reducer comprises the following steps: the invention adopts C3-C6 alkyl silane coupling agent to pretreat distillation residues, and the distillation residues are doped into naphthalene oil to be used as naphthalene-containing raw material to prepare the naphthalene water reducer, which not only has lower bleeding rate, but also has higher water reducing rate and plastic retention performance. The preparation method is simple to operate, reaction conditions are easy to control, and distillation residues are used as raw materials, so that the production cost of the naphthalene water reducer is reduced, and the environmental pollution is reduced.)

1. The preparation method of the environment-friendly naphthalene water reducer is characterized by comprising the following steps:

step (1): grinding and screening the distillation residues, placing the distillation residues in a reaction container, heating to 80-100 ℃, adding a modifier into the reaction container, and keeping the temperature for 0.5-1 h under the stirring action to obtain a distillation residue pretreatment substance;

step (2): adding naphthalene oil into the distillation residue pretreatment obtained in the step (1), heating to 150-160 ℃, then dropwise adding a sulfonating agent into the distillation residue pretreatment, controlling the dropwise adding speed, and keeping the temperature for 2-5 hours after dropwise adding is finished to obtain a sulfonated material;

and (3): when the temperature of the sulfonated material obtained in the step (2) is reduced to 110-120 ℃, adding water into the sulfonated material, controlling the water addition amount, keeping the temperature for 0.1-0.3 h, then dropwise adding an aldehyde compound into the sulfonated material, controlling the dropwise adding speed, finishing dropwise adding within 1-3 h, and keeping the temperature for 1-3 h after dropwise adding is finished to obtain a condensed material;

and (4): and (4) when the temperature of the condensation material obtained in the step (3) is reduced to 80-90 ℃, dropwise adding a pH regulator into the condensation material until the pH is 7-10 to obtain the environment-friendly naphthalene water reducer.

2. The preparation method of the environment-friendly naphthalene water reducer according to claim 1, wherein the modifier in the step (1) is a C3-C6 alkylsilane coupling agent.

3. The preparation method of the environment-friendly naphthalene water reducer according to claim 1, characterized in that the mass ratio of the distillation residues to the modifier in the step (1) is 1: (0.05-0.12).

4. The preparation method of the environment-friendly naphthalene water reducer according to claim 1, wherein the mass ratio of the naphthalene oil to the distillation residue pretreatment substance in the step (2) is (1.3-1.8): 1.

5. the preparation method of the environment-friendly naphthalene water reducer according to claim 1, wherein the mass ratio of the sulfonating agent to the distillation residue pretreatment substance in the step (2) is (2-2.5): 1.

6. the preparation method of the environment-friendly naphthalene water reducer according to claim 1, wherein the sulfonating agent is added dropwise in 20-40 min in step (2).

7. The preparation method of the environment-friendly naphthalene water reducer according to claim 1, characterized in that the water addition amount in the step (3) is controlled to be 0.05-0.1 times of the mass of the sulfonated material.

8. The preparation method of the environment-friendly naphthalene water reducer according to claim 1, wherein the mass of the aldehyde compound in the step (3) is 0.20-0.25 times that of the sulfonated material.

9. The preparation method of the environment-friendly naphthalene water reducer according to claim 1, wherein the pH regulator in the step (4) is 32 wt% liquid caustic soda.

10. The application of the environment-friendly naphthalene water reducer prepared by the preparation method of the environment-friendly naphthalene water reducer according to any one of claims 1 to 9 is characterized in that the environment-friendly naphthalene water reducer is used as an additive of high-performance concrete.

Technical Field

The invention relates to the technical field of building materials, in particular to a preparation method of an environment-friendly naphthalene water reducer.

Background

The naphthalene water reducer is a concrete admixture which is most widely used at present, and is often used for preparing high-fluidity, high-strength and high-performance concrete. At present, due to the increasing production of concrete, the demand of industrial naphthalene is increasing, and the phenomenon of industrial naphthalene shortage appears on the global scale, so that an environment-friendly and economic naphthalene-containing raw material is urgently required to replace industrial naphthalene to produce the naphthalene water reducing agent. Meanwhile, 2-naphthol can produce a large amount of distillation residues in the production and preparation process, the main components of the distillation residues are organic compounds containing naphthalene, including 1-naphthol, 1-naphthol-2-naphthol condensation compounds, naphthalene sulfonate and the like, the existing treatment method is to discharge the distillation residues to a boiler, the cooled residues are packaged by asphalt and sold, or related units are directly consigned to treat in the form of waste, so that the economic value is low, and the environment is seriously polluted.

The naphthalene oil is coal tar distillate with distillation range of 210-230 ℃ in the process of preparing industrial naphthalene or refined naphthalene, wherein the naphthalene content is 40-95%, and the naphthalene oil also contains a small amount of phenols, indole and other compounds with complex components. Because the boiling points are close, the components are complex and difficult to separate and purify, and secondary pollution is caused to the environment.

The applicant finds that when the distillation residue of the 2-naphthol is used as a raw material to produce the naphthalene water reducer, compared with the conventional water reducer, the naphthalene water reducer can improve the water reducing rate and improve the slump, but has the problems that on one hand, the distillation residue is dark in color, the reaction degree is not easy to observe and control in the sulfonation and condensation reaction processes, the performance of the prepared water reducer is unstable, and on the other hand, most of the distillation residue is organic compounds with conjugated structures, so that the prepared water reducer is not easy to disperse in the preparation process of the water reducer, and when the prepared water reducer is used for concrete mixtures, although the prepared water reducer has good water reducing rate and slump, the bleeding phenomenon is easy to occur, and the working performance and the reliability of concrete are influenced.

Disclosure of Invention

In order to solve the technical problems, the invention provides a preparation method of an environment-friendly naphthalene water reducer, which comprises the following steps:

step (1): grinding and screening the distillation residues, placing the distillation residues in a reaction container, heating to 80-100 ℃, adding a modifier into the reaction container, and keeping the temperature for 0.5-1 h under the stirring action to obtain a distillation residue pretreatment substance;

step (2): adding naphthalene oil into the distillation residue pretreatment obtained in the step (1), heating to 150-160 ℃, then dropwise adding a sulfonating agent into the distillation residue pretreatment, controlling the dropwise adding speed, and keeping the temperature for 2-5 hours after dropwise adding is finished to obtain a sulfonated material;

and (3): cooling the sulfonated material obtained in the step (2) to 110-120 ℃, adding water into the sulfonated material, controlling the water addition amount, keeping the temperature for 0.1-0.3 h, then dropwise adding an aldehyde compound into the sulfonated material, controlling the dropwise adding speed, finishing dropwise adding within 1-3 h, and keeping the temperature for 1-3 h after dropwise adding is finished to obtain a condensed material;

and (4): and (4) when the temperature of the condensation material obtained in the step (3) is reduced to 80-90 ℃, dropwise adding a pH regulator into the condensation material until the pH is 7-10 to obtain the environment-friendly naphthalene water reducer.

As a preferable technical scheme of the invention, the modifier in the step (1) is a C3-C6 alkyl silane coupling agent.

In a preferred embodiment of the present invention, the mass ratio of the distillation residue to the modifier in the step (1) is 1: (0.05-0.12).

As a preferable technical scheme of the invention, the mass ratio of the naphthalene oil to the distillation residue pretreatment substance in the step (2) is (1.3-1.8): 1.

in a preferable technical scheme of the invention, the mass ratio of the sulfonating agent to the distillation residue pretreatment substance in the step (2) is (2-2.5): 1.

as a preferable technical scheme, the sulfonating agent is added dropwise in the step (2) within 20-40 min.

As a preferable technical scheme, the water adding amount in the step (3) is controlled to be 0.05-0.1 time of the mass of the sulfonated material.

As a preferable technical scheme of the invention, the mass of the aldehyde compound in the step (3) is 0.20-0.25 time of that of the sulfonated material.

As a preferable technical scheme of the invention, the pH regulator in the step (4) is 32 wt% of liquid alkali.

The invention provides an application of the environment-friendly naphthalene water reducer prepared by the preparation method of the environment-friendly naphthalene water reducer, and the environment-friendly naphthalene water reducer is used as an additive of high-performance concrete.

Has the advantages that: the invention provides a preparation method of an environment-friendly naphthalene water reducer, which is characterized in that distillation residues are pretreated by adopting an alkyl silane coupling agent of C3-C6 and doped into naphthalene oil as a naphthalene-containing raw material, and the prepared naphthalene water reducer has low bleeding rate, high water reducing rate and high plasticity-maintaining performance. The preparation method is simple to operate, reaction conditions are easy to control, and distillation residues are used as raw materials, so that the production cost of the naphthalene water reducer is reduced, and the environmental pollution is reduced.

Description of the drawings:

FIG. 1 is an FTIR test chart of the distillation residue in the examples of the present invention, FIG. 2 is a GC-MS test chart of the distillation residue, FIG. 3 is an NMR test chart of the distillation residue, FIG. 4 is an XRD test chart of the distillation residue ash, and FIG. 5 is a TGA test chart of the distillation residue.

Detailed Description

The disclosure may be understood more readily by reference to the following detailed description of preferred embodiments of the invention and the examples included therein. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control.

The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.

When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when a range of "1 to 5" is disclosed, the described range should be interpreted to include the ranges "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.

In addition, the indefinite articles "a" and "an" preceding an element or component of the invention are not intended to limit the number requirement (i.e., the number of occurrences) of the element or component. Thus, "a" or "an" should be read to include one or at least one, and the singular form of an element or component also includes the plural unless the stated number clearly indicates that the singular form is intended.

In order to solve the technical problems, the invention provides a preparation method of an environment-friendly naphthalene water reducer, which comprises the following steps:

step (1): grinding and screening the distillation residues, placing the distillation residues in a reaction container, heating to 80-100 ℃, adding a modifier into the reaction container, and keeping the temperature for 0.5-1 h under the stirring action to obtain a distillation residue pretreatment substance;

step (2): adding naphthalene oil into the distillation residue pretreatment obtained in the step (1), heating to 150-160 ℃, then dropwise adding a sulfonating agent into the distillation residue pretreatment, controlling the dropwise adding speed, and keeping the temperature for 2-5 hours after dropwise adding is finished to obtain a sulfonated material;

and (3): when the temperature of the sulfonated material obtained in the step (2) is reduced to 110-120 ℃, adding water into the sulfonated material, controlling the water addition amount, keeping the temperature for 0.1-0.3 h, then dropwise adding an aldehyde compound into the sulfonated material, controlling the dropwise adding speed, finishing dropwise adding within 1-3 h, and keeping the temperature for 1-3 h after dropwise adding is finished to obtain a condensed material; preferably, during the processes of adding the aldehyde compound, keeping the temperature, and the like, if the material is particularly viscous, a small amount of water is added for many times;

and (4): and (4) when the temperature of the condensation material obtained in the step (3) is reduced to 80-90 ℃, dropwise adding a pH regulator into the condensation material until the pH is 7-10 to obtain the environment-friendly naphthalene water reducer.

And (3) adding a small amount of water for many times during the dropwise adding and heat preservation of the system in the step (3) if the material is particularly viscous.

In a preferred embodiment, the preparation method comprises the following steps:

step (1): grinding and screening the distillation residues, placing the distillation residues in a reaction container, heating to 90 ℃, adding a modifier into the reaction container, and keeping the temperature for 0.6h under the stirring action to obtain a distillation residue pretreatment substance;

step (2): adding naphthalene oil into the distillation residue pretreatment obtained in the step (1), heating to 155 ℃, then dropwise adding a sulfonating agent into the distillation residue pretreatment, controlling the dropwise adding speed, and keeping the temperature for 3 hours after dropwise adding is finished to obtain a sulfonated material;

and (3): when the temperature of the sulfonated material obtained in the step (2) is reduced to 115 ℃, adding water into the sulfonated material, controlling the water addition amount, keeping the temperature for 0.2h, then dropwise adding an aldehyde compound into the sulfonated material, controlling the dropwise adding speed, finishing dropwise adding within 1-3 h, and keeping the temperature for 2h after dropwise adding is finished to obtain a condensed material;

and (4): and (4) when the temperature of the condensation material obtained in the step (3) is reduced to 80 ℃, dropwise adding a pH regulator into the condensation material until the pH is 7-10 to obtain the environment-friendly naphthalene water reducer.

The distillation residue is not particularly limited, and the solid waste produced in the process of producing 2-naphthol can be selected from commercially available raw materials, including but not limited to products of Wooder technologies Co., Ltd, Schoik, etc., and the main components of the product include 4.0 to 5.0 wt% of 1-naphthol (CAS number: 90-15-3), 6.0 to 7.0 wt% of 2-naphthol (CAS number: 135-19-3), 10.0 to 11.0 wt% of 1-naphthol-2-naphthol condensate (CAS number: 611-49-4), 6.0 to 7.0 wt% of N-methyl saccharin (CAS number: 602-09-5), 6.0 to 7.0 wt% of benzanthracene-7, 12-dione (CAS number: 2498-66-0), and 5.0 to 6.0 wt% of naphthalene (CAS number: 91-20-3), 9.0 to 10.0 wt% of 1,1 '-binaphthyl (CAS number: 604-53-5), 8.0 to 9.0 wt% of 1, 1' -bi-2-naphthol (CAS number: 602-09-5), 27.0 to 28.0 wt% of naphthalene sulfonate, 6.0 to 7.0 wt% of Dinaphylo (1,2-b:1 ', 2' -d) furan (CAS number: 207-93-2), and 6.0 to 10.0 wt% of other auxiliaries including 8-isoproyl-1, 3-dimethyl-phenanthrene (CAS number: 135886-06-5), 5,6,6 ', 11, 12' -Hexahydro-6 ', 12' -methyl-chrysene-5, 11-dione (CAS number: 111977-22-1), 4H-1-Benzopyran-4-dione, 2- (3, 3-yl) -3,7-dimethoxy (CAS number: 17093-86-6), 6-hydroxyflexor (CAS number: 37515-51-8).

The sulfonating agent is selected from at least one of concentrated sulfuric acid, sodium sulfite and sodium pyrosulfite; preferably, the sulfonating agent is concentrated sulfuric acid with the concentration of 98 wt%.

The aldehyde compound in the invention is at least one selected from formaldehyde, acetaldehyde and propionaldehyde; preferably, the aldehyde compound is formaldehyde.

In some embodiments, the modifier in step (1) is a C3 to C6 alkylsilane coupling agent. Examples of the C3-C6 alkylsilane coupling agent include, but are not limited to, propyltriethoxysilane (CAS number: 2550-02-9), butyltriethoxysilane (CAS number: 4781-99-1), isobutyltriethoxysilane (CAS number: 17980-47-1), (3, 3-dimethylbutyl) triethoxysilane (CAS number: 41966-94-3), pentyltriethoxysilane (CAS number: 2761-24-2), hexyltriethoxysilane (CAS number: 18166-37-5); preferably, the C3-C6 alkylsilane coupling agent is (3, 3-dimethylbutyl) triethoxysilane.

In some embodiments, the mass ratio of the distillation residue to the modifier in step (1) is 1: (0.05 to 0.12); preferably, the mass ratio of the distillation residue to the modifier in the step (1) is 1: 0.10.

the applicant unexpectedly finds that compared with the conventional naphthalene water reducer, the water reducer prepared by directly using naphthalene oil as a naphthalene-containing raw material and doping partial distillation residues generated in the production process of 2-naphthol and directly performing sulfonation, condensation, neutralization and the like has higher water reducing rate and better slump of the concrete when leaving the factory. However, there is a problem in that the concrete is liable to suffer severe bleeding with time. The applicant unexpectedly finds that the prepared water reducing agent can effectively avoid serious bleeding phenomenon after distillation residues are pretreated by taking an alkyl silane coupling agent as a modifier, particularly, when the carbon atom number of an alkyl chain is 3-6, the bleeding rate is low, relatively high water reducing rate and slump can still be ensured, and under the condition that the carbon atom number of the alkyl chain is the same, the water reducing agent prepared from the distillation residues pretreated by the alkyl silane coupling agent with a branched chain has better bleeding prevention performance and has no influence on the original high water reducing rate and slump. Presumably, molecular chains with certain length and siloxane groups are grafted in a molecular structure with conjugated bonds in the distillation residues, so that water reducing agent molecules can be better adsorbed on the surfaces of cement particles in the initial stage of hydration to form an adsorption double electric layer, capillary pores in concrete are effectively blocked, and bleeding is prevented.

In some embodiments, the mass ratio of the naphthalene oil to the distillation residue pretreatment in the step (2) is (1.3-1.8): 1; preferably, the mass ratio of the naphthalene oil to the distillation residue pretreatment in the step (2) is 1.6: 1.

in some embodiments, the mass ratio of the sulfonating agent to the distillation residue pretreatment in step (2) is (2-2.5): 1; preferably, the mass ratio of the sulfonating agent to the distillation residue pretreatment in the step (2) is 2.2: 1.

in some embodiments, the sulfonating agent is added dropwise in the step (2) within 20-40 min.

In some embodiments, the water adding amount in the step (3) is controlled to be 0.05-0.1 time of the mass of the sulfonated material; preferably, the water adding amount in the step (3) is controlled to be 0.06 time of the mass of the sulfonated material.

According to the invention, the main component content of the distillation residue is combined, and the change of acidity in the whole system is in a stable and controllable trend by controlling the dosage, the dropping speed and the water adding amount of the sulfonating agent, so that the sulfonation degree can be controlled conveniently, and the generation of byproducts which are not beneficial to the subsequent condensation reaction can be avoided.

In some embodiments, the aldehyde compound in the step (3) is 0.20-0.25 times of the mass of the sulfonated material; preferably, the aldehyde compound in the step (3) is 0.22 times of the mass of the sulfonated material.

In some embodiments, the pH adjusting agent in step (4) is 32 wt% liquid alkali. In order to ensure the stability of the water reducing agent, the step (4) of the invention adopts segmented neutralization treatment, namely when the temperature of the condensation material obtained in the step (3) is reduced to 80-90 ℃, a pH regulator is dripped into the condensation material until the pH is 7-10, preferably 7-8, and the environment-friendly naphthalene water reducing agent is prepared.

The second aspect of the invention provides an application of the environment-friendly naphthalene water reducer prepared by the preparation method of the environment-friendly naphthalene water reducer, and the environment-friendly naphthalene water reducer is used as an additive of high-performance concrete.

Compared with the conventional naphthalene water reducer prepared by taking industrial naphthalene as a raw material, the naphthalene water reducer prepared by pretreating the distillation residue waste of the 2-naphthol and then doping the distillation residue waste into naphthalene oil has higher or equivalent water reducing rate, improves the plasticity retention performance of concrete, effectively avoids bleeding phenomenon and can be used as an additive of high-performance concrete.

The naphthalene oil can be a commercial product, and the naphthalene content of the naphthalene oil can be 45-95%.

In the third step of the following examples, water is added in a small amount for many times during the addition of the aldehyde compound, the heat preservation reaction, and the like, if the material is particularly viscous. The distillation residues in all the examples of the invention are from Schoik-Ward chemical technology, Inc., and the composition analysis maps thereof are shown in the attached figures 1-5; the naphthalene oil is derived from 210-230 ℃ fraction residue in the process of preparing refined naphthalene from industrial naphthalene by Showa Ward chemical technology Co., Ltd, and the naphthalene content is 85 percent; the formaldehyde content is 35-37 wt%.