CN115215566A

CN115215566A - Liquid cement metal ion remover and preparation method thereof

Info

Publication number: CN115215566A
Application number: CN202111140466.8A
Authority: CN
Inventors: 鲁昌宝
Original assignee: Individual
Current assignee: Individual
Priority date: 2021-09-28
Filing date: 2021-09-28
Publication date: 2022-10-21

Abstract

The invention relates to the field of C04B7/42, in particular to a liquid cement metal ion remover and a preparation method thereof. The liquid cement metal ion remover comprises the following raw materials in parts by weight: 10-20 parts of reducing agent, 4-10 parts of metal salt, 1-3 parts of stabilizer, 3-6 parts of assistant, 1-5 parts of catalyst and 60-80 parts of liquid solvent. The remover prepared by the method has good chromium element removing performance, effectively reduces a cement alkaline system, is suitable for popularization in the field of cement processing, and has wide development prospect.

Description

Liquid cement metal ion remover and preparation method thereof

Technical Field

The invention relates to the field of C04B7/42, in particular to a liquid cement metal ion remover and a preparation method thereof.

Background

Portland cement is a cement raw material which can be frequently used in daily production and living construction, and in the production process of Portland cement, a chromium metal raw material is an inevitable trace element in Portland cement. In the process of calcining cement, chromium metal elements can generate hexavalent chromium with extremely high toxicity and pollution properties along with the formation of oxidizing and alkaline conditions, which causes the production process of cement to have great negative effects on the environment, so that how to reduce the formation of hexavalent chromium in the production process of portland cement becomes a hotspot of research in recent years.

The high-efficiency liquid cement chromium removal agent provided by the prior art (CN 202010225054.3) is mainly used for rapid dispersion and reaction of chromium elements by using a reducing agent, a precipitating agent, a catalyst and other raw materials, thereby effectively ensuring the chromium removal efficiency; however, in actual use, the dispersion effect of the chromium removing agent in the cement system is not good enough, and the optimal chromium removing effect of the cement cannot be obtained.

Therefore, there is a need for a metal ion remover that has the rapid dispersion and reactivity of chromium element and also can effectively disperse in cement systems and reduce environmental impact.

Disclosure of Invention

In order to solve the problems, the invention provides a liquid cement metal ion remover in a first aspect, which comprises the following raw materials in parts by weight: 10-20 parts of reducing agent, 4-10 parts of metal salt, 1-3 parts of stabilizer, 3-6 parts of assistant, 1-5 parts of catalyst and 60-80 parts of liquid solvent.

As a preferred scheme, the reducing agent is at least one of sodium metabisulfite, sodium sulfite, ammonium sulfite, sodium sulfide, sodium hydrosulfide, sulfur dioxide, ferrous chloride and ammonium sulfide.

As a preferred scheme, the reducing agent is sodium sulfite and ferrous chloride; the mass ratio of the sodium sulfite to the ferrous chloride is 6-10: 3 to 5.

As a preferable scheme, the mass ratio of the sodium sulfite to the ferrous chloride is 8-9: 4.

in a preferred embodiment, the metal salt is at least one of zinc sulfate, zinc chloride, ferric sulfate, ferrous sulfate, polyaluminum chloride, magnesium sulfate, aluminum potassium sulfate and aluminum sulfate.

In a preferred embodiment, the metal salts are zinc chloride and iron sulfate.

Preferably, the mass ratio of the zinc chloride to the ferric sulfate is 1.

In a preferred embodiment, the catalyst is at least one of a titanium-based catalyst or an antimony-based catalyst.

In a preferred embodiment, the catalyst is titanium sulfate.

In a preferred embodiment, the stabilizer is at least one of polyacrylate, ascorbic acid, sodium carbonate, sodium acetate, ammonium acetate, phenylalanine, alcohol ether carboxylate and sugar acid.

As a preferred embodiment, the stabilizer is an alcohol ether carboxylate and a sugar acid.

As a preferred embodiment, the alcohol ether carboxylate is sodium ceteth-13 carboxylate.

As a preferred embodiment, the sugar acid is gluconic acid.

As a preferred scheme, the mass ratio of the sodium ceteth-13 carboxylate to the gluconic acid is 1.

In a preferred embodiment, the auxiliary agents are citric acid, secondary alcohol polyoxyethylene ether and cocobetaine.

As a preferable scheme, the mass ratio of the citric acid, the secondary alcohol polyoxyethylene ether and the coco betaine is 10-12: 3-4.

As a preferable scheme, the mass ratio of the citric acid, the secondary alcohol polyoxyethylene ether and the cocobetaine is 11.

In the application, the dispersibility of the remover system in a water system is effectively improved by controlling the compounding ratio of citric acid, secondary alcohol polyoxyethylene ether and coco-betaine, and the stability and the removal efficiency of the remover are also effectively improved. The applicant speculates that: under the compounding ratio, the secondary alcohol polyoxyethylene ether can form effective colloid protection on the coco-betaine, reduce the phenomenon of ion neutralization in an acid system, and effectively reduce the alkaline condition of a cement system due to the occurrence of the acid system.

In a preferred embodiment, the liquid solvent is an aqueous solution of sodium bicarbonate.

The second aspect of the present invention provides a method for preparing the above liquid cement metal ion remover, which at least comprises the following steps: (1) Firstly, adding a liquid solvent into a reaction kettle, uniformly adding 50wt% of a reducing agent and a stabilizing agent for three times, and stirring for 2-3 minutes at intervals when the materials are put into the kettle each time; (2) Adding the residual reducing agent into the reaction kettle, and stirring for 5-6 minutes; (3) And (3) putting the catalyst into the kettle and stirring for 5-6 minutes, adding the auxiliary agent into the kettle and stirring for 5-6 minutes, and finally adding the metal salt into the kettle and stirring for 5-6 minutes to obtain the catalyst.

Has the advantages that:

1. the liquid cement metal ion remover disclosed by the invention is in a liquid form as a whole through the adjustment of a formula, has a good storage advantage compared with a common powder cement metal remover, is easier to go deep into a porous system of cement, and has an obvious use advantage.

2. Through the synergistic use of a plurality of surface active substances in the auxiliary agent, the surface tension of the system and the cement system is reduced, the permeation and dispersion efficiency is improved, the inactivation of the surface active substances in the system can be reduced, and the alkaline condition of the cement system is effectively reduced.

Detailed Description

Example 1

The first aspect of embodiment 1 provides a liquid cement metal ion remover, which comprises the following raw materials in parts by weight: 15 parts of reducing agent, 6 parts of metal salt, 2 parts of stabilizing agent, 5 parts of auxiliary agent, 3 parts of catalyst and 70 parts of liquid solvent.

In this embodiment, the reducing agent is sodium sulfite and ferrous chloride, and the mass ratio is 9.

In this example, the metal salt is zinc chloride and ferric sulfate, and the mass ratio is 1.

In this example, the catalyst was titanium sulfate.

In the embodiment, the stabilizer is sodium ceteth-13 carboxylate and gluconic acid, and the mass ratio is 1.

In the embodiment, the auxiliary agents are citric acid, secondary alcohol polyoxyethylene ether and coco betaine, and the mass ratio of the citric acid to the secondary alcohol polyoxyethylene ether to the coco betaine is 11.

In this embodiment, the liquid solvent is an aqueous solution of sodium bicarbonate, and the mass percentage of the sodium bicarbonate is 2%.

In this example, cocobetaine is a product of cocamidopropyl betaine CAB-35 sold by southbound runfeng petrochemical limited.

In the embodiment, the secondary alcohol polyoxyethylene ether is a secondary alcohol polyoxyethylene ether AEO-9 product sold by Shandong Leon New Material company Limited.

In a second aspect, this embodiment provides a method for preparing the above liquid cement metal ion remover, which comprises the following steps: (1) Firstly, adding a liquid solvent into a reaction kettle, uniformly adding 50wt% of a reducing agent and a stabilizing agent for three times, and stirring for 2.5 minutes at intervals when the materials are put into the kettle every time; (2) Adding the residual reducing agent into the reaction kettle, and stirring for 5 minutes; (3) And (3) adding the catalyst into the kettle, stirring for 5 minutes, adding the auxiliary agent into the kettle, stirring for 5 minutes, and finally adding the metal salt into the kettle, and stirring for 5 minutes to obtain the catalyst.

Example 2

The embodiment of the present invention is different from embodiment 1 in that: 12 parts of reducing agent, 5 parts of metal salt and 3 parts of stabilizing agent.

Comparative example 1

The embodiment of this comparative example is the same as example 1 except that: the mass ratio of sodium sulfite to ferrous chloride is 1.

Comparative example 2

The embodiment of this comparative example is the same as example 1 except that: the mass ratio of sodium ceteth-13 carboxylate to gluconic acid was 0.

Comparative example 3

The embodiment of this comparative example is the same as example 1 except that: the mass ratio of the citric acid to the secondary alcohol polyoxyethylene ether to the coco betaine is 10.

Evaluation of Performance

The chromium removal effect is as follows: PC42.5R cement (clinker 83%, limestone 5%, fly ash 6%, gypsum 6%) sold by the XNSN group was treated with the remover prepared in examples and comparative examples, and the effect of removing chromium was tested by referring to the test method of GB31893-2015, 5 samples were tested in each example comparative example, and the average value of the measured values is shown in Table 1.

TABLE 1

Examples	Hexavalent chromium/pp
		Example 1	1.2
Example 2	1.3
		Comparative example 1	3.7
Comparative example 2	4.1
		Comparative example 3	3.9

Through the embodiments 1-2, the comparative examples 1-3 and the table 1, the remover prepared by the liquid cement metal ion remover and the preparation method thereof provided by the invention have good chromium element removal performance, effectively reduce a cement alkaline system, are suitable for popularization in the field of cement processing, and have wide development prospects. Wherein, the example 1 obtains the best performance index under the factors of the best preparation raw material proportion, the best preparation process and the like.

Claims

1. A liquid cement metal ion remover is characterized in that: the raw materials at least comprise the following components in parts by weight: 10-20 parts of reducing agent, 4-10 parts of metal salt, 1-3 parts of stabilizer, 3-6 parts of assistant, 1-5 parts of catalyst and 60-80 parts of liquid solvent.

2. The liquid cement metal ion remover according to claim 1, characterized in that: the reducing agent is at least one of sodium metabisulfite, sodium sulfite, ammonium sulfite, sodium sulfide, sodium hydrosulfide, sulfur dioxide, ferrous chloride and ammonium sulfide.

3. The liquid cement metal ion remover according to claim 2, characterized in that: the reducing agent is sodium sulfite and ferrous chloride; the mass ratio of the sodium sulfite to the ferrous chloride is 6-10: 3 to 5.

4. The liquid cement metal ion remover according to any one of claims 1 to 3, characterized in that: the metal salt is at least one of zinc sulfate, zinc chloride, ferric sulfate, ferrous sulfate, polyaluminium chloride, magnesium sulfate, aluminum potassium sulfate and aluminum sulfate.

5. The liquid cement metal ion remover according to any one of claims 1 to 4, characterized in that: the catalyst is at least one of a titanium catalyst or an antimony catalyst.

6. The liquid cement metal ion remover according to any one of claims 1 to 5, characterized in that: the stabilizer is at least one of polyacrylate, ascorbic acid, sodium carbonate, sodium acetate, ammonium acetate, phenylalanine, alcohol ether carboxylate and sugar acid.

7. The liquid cement metal ion remover according to any one of claims 1 to 6, characterized in that: the auxiliary agents are citric acid, secondary alcohol polyoxyethylene ether and coco betaine.

8. The liquid cement metal ion remover according to claim 7, characterized in that: the mass ratio of the citric acid, the secondary alcohol polyoxyethylene ether and the cocoyl betaine is 10-12: 3-4.

9. The liquid cement metal ion remover according to any one of claims 1 to 8, characterized in that: the liquid solvent is an aqueous sodium bicarbonate solution.

10. A method for preparing a liquid cement metal ion remover according to any one of claims 1 to 9, characterized by: the steps at least comprise the following steps: (1) Firstly, adding a liquid solvent into a reaction kettle, uniformly adding 50wt% of a reducing agent and a stabilizing agent for three times, and stirring for 2-3 minutes at intervals when the materials are put into the kettle each time; (2) Adding the residual reducing agent into the reaction kettle, and stirring for 5-6 minutes; (3) And (3) putting the catalyst into the kettle and stirring for 5-6 minutes, adding the auxiliary agent into the kettle and stirring for 5-6 minutes, and finally adding the metal salt into the kettle and stirring for 5-6 minutes to obtain the catalyst.