阅读说明：本技术 一种用酸洗磷化废渣制混凝土保塑剂的制备方法 (Preparation method for preparing concrete plastic retaining agent by using acid pickling phosphorization waste residues ) 是由 毕万利 孙明晶 关岩 张毅 孙美硕 于 2021-09-08 设计创作，主要内容包括：本发明属于混凝土添加剂制造技术领域,具体涉及一种用酸洗磷化废渣制混凝土保塑剂的制备方法,其特征在于,各组份按重量份比计,包括磷酸铁废渣、铁尾矿粉、葡萄糖酸钠。制备过程包括均化混合、活化烘干和计量包装,即得到混凝土保塑剂成品。与现有技术相比,本发明的优点是：1)达到了危废物质的资源化利用,产品应用在混凝土中对抗渗、凝结及工作性能有一定的好处,使混凝土浆体的水化速度变慢,延长水化硬化过程和时间,减缓坍落度损失,成本相应降低。2)抗压强度达到35.8～36.5MPa；静态凝结时间延长至120 min,安定性合格,混凝土2小时坍落度损失25～30毫米,满足了混凝土的坍落度保持性能。(The invention belongs to the technical field of concrete additive manufacturing, and particularly relates to a preparation method of a concrete plastic-retaining agent by using acid-washing phosphated waste residues. The preparation process comprises homogenizing, mixing, activating, drying, metering and packaging to obtain the finished product of the concrete plasticity-maintaining agent. Compared with the prior art, the invention has the advantages that: 1) the product has certain advantages of impermeability, condensation and working performance when being applied to concrete, so that the hydration speed of concrete slurry is slowed down, the hydration hardening process and time are prolonged, the slump loss is slowed down, and the cost is correspondingly reduced. 2) The compressive strength reaches 35.8-36.5 MPa; the static setting time is prolonged to 120min, the stability is qualified, and the slump loss of the concrete is 25-30 mm after 2 hours, so that the slump retention performance of the concrete is met.)

1. A preparation method for preparing a concrete plastic-retaining agent by using acid-washing phosphated waste residues is characterized by comprising the following components in parts by weight: 70-70.5 parts of iron phosphate waste residues, 29-29.66 parts of iron tailing powder and 0.34-1 part of sodium gluconate.

2. The method for preparing the concrete plasticity-maintaining agent by using the acid-washing phosphated waste residues as claimed in claim 1, wherein the iron phosphate waste residues are obtained from steel rolling enterprises adopting a phosphate rust removal process, and the iron phosphate waste residues comprise the following chemical components in percentage by mass: h₂PO₄ 5~9.5%、SC（NH₂）₂ 0.1~0.5%、FePO₄·2H₂O 90~94.5%。

3. The method for preparing the concrete plastic-retaining agent by using the acid-washing phosphated waste residues as claimed in claim 1, wherein the iron tailing powder is obtained from washed fine sand type iron tailings, and the chemical components of the iron tailing powder by mass percent are as follows: SiO 2₂68.68%、CaO 5.25%、MgO 5.57%、Fe₂O₃15.13%、Al₂O₃2.97%, the balance 2.4% being inevitable impurities, the ignition loss being 1.12%.

4. The method for preparing the concrete plasticity-maintaining agent from the acid pickling phosphorization waste residues as claimed in claim 1, wherein the sodium gluconate is of industrial purity.

5. The preparation method of the concrete plasticity-maintaining agent by using the acid pickling phosphorization waste residue as claimed in claim 1, wherein the preparation process comprises homogenizing, mixing, activating, drying and metering and packaging, and specifically comprises the following steps:

1) homogenizing and mixing, namely mixing the iron phosphate waste residues, the iron tailing powder and the sodium gluconate with the formula ratio in proportion, and continuously homogenizing and stirring the mixture by using an air-mechanical composite mixer at the linear speed of 4000-6000 mm/min to obtain a mixture with the homogenizing coefficient = 1-1.8;

2) activating and drying, namely feeding the mixture into an activating and drying mill with an activating ring and an activating lining plate, and heating to 60-85 ℃ by self friction of the mixture so that thiourea and phosphoric acid in the mixture continue to react with Fe in the waste residue₂O₃Mixing to generate iron phosphate, removing thiourea and phosphoric acid, and pressing and grinding into a storage bin through negative pressure after the activated powder is qualified in granularity;

3) and (4) metering and packaging, namely, after the concrete is metered by a bucket scale, automatically packaging into bags by a rotary packaging machine to obtain the finished product of the concrete plasticity-maintaining agent.

6. The method for preparing the concrete plastic-retaining agent from the acid pickling phosphorization waste residues as claimed in claim 5, wherein the density of the finished concrete plastic-retaining agent is 1.25-1.63 g/cm3, and the screen residue of a square-hole screen with the granularity of 0.08mm is less than 10%; initial setting time difference is plus 60 to plus 120min, the compressive strength ratio is 95 percent in 7 days, the compressive strength ratio is 120 percent in 28 days, and the softening coefficient is 0.55.

7. The preparation method of the concrete plasticity-maintaining agent from the acid pickling phosphorization waste residues according to claim 5, wherein the addition amount of the finished concrete plasticity-maintaining agent is that 14-22 kg of the plasticity-maintaining agent is directly added into each ton of concrete in the common pumping agent compounding process, and is 3.5-5.5% of the using amount of the cementing material.

8. The method for preparing the concrete plasticity-maintaining agent from the acid pickling phosphorization waste residues according to claim 5, wherein the addition amount of the finished concrete plasticity-maintaining agent is 5-5.5% of the amount of the cementing material in the range of the ambient temperature of more than 20-35 ℃; the addition amount is 3.5-4.0% of the dosage of the cementing material in the range of the environmental temperature of 10-20 ℃.

Technical Field

The invention belongs to the technical field of concrete additive manufacturing, and particularly relates to a preparation method for preparing a concrete plasticity-maintaining agent by using acid-washing phosphated waste residues.

Technical Field

The pickling phosphorization waste residue is obtained by adopting a pickling phosphorization one-step method, and when the steel is pickled, oxide skin and iron rust (Fe) are continuously dissolved in a pickling solution₂O₃) And then produced. When Fe²⁺When the ion concentration reaches saturation, the acid pickling phosphating solution loses the capability of dissolving oxide skin, and generally, oxidants such as hydrogen peroxide and the like are added to reduce Fe²⁺The concentration of the ions enables the phosphating solution to continue to play its role, and 0.05 ton of iron phosphate waste residue is precipitated and needs to be separated out when pickling and dipping one ton of steel. The waste iron phosphate residues are generally treated by landfill, not only can land be occupied, but also harmful substances in the waste iron phosphate residues can permeate underground to enter biological circulation, and finally the waste iron phosphate residues are enriched in human bodies and harmful to human health and are HW17 type wastes in national hazardous material records.

The main components of the acid pickling phosphorization waste residue are iron dihydrogen phosphate, zinc dihydrogen phosphate and the like, and are mainly sediments generated by reaction with steel. The method has the advantages that the method carries out resource treatment on the phosphatized waste residues, extracts useful resources in the phosphatized waste residues for reuse, avoids resource waste, and makes many explorations for scientific and technological workers for many years. Such as: 1) reacting iron phosphate with caustic soda to generate sodium phosphate. Several assistants such as sodium phosphate, sodium silicate and composite surfactant are added to prepare the detergent with good oil-removing effect. 2) Adding hydrochloric acid into the ferric hydroxide precipitate to generate ferric chloride, adding flocculation aid, and making into water treatment agent. 3) Or the ferric hydroxide precipitate generated by the reaction is subjected to thermal decomposition reaction to generate ferric oxide, so as to produce the ferric oxide red.

The concrete plasticity-maintaining agent is one kind of additive capable of reducing slump loss of concrete in certain time interval and has the main function of regulating the compatibility and adaptability of the additive and cement. The concrete is suitable for high-temperature season construction, long-distance transportation, ultra-high range pumping and cast-in-place concrete; the concrete has the advantages of large volume, self-leveling concrete, high-strength and high-performance concrete and the like, can enable the fresh concrete to have good workability, and can enable the concrete to obtain better slump retentivity. Is prepared from various additives such as naphthalene series, aliphatic series, amino, polycarboxylic acid and the like.

Disclosure of Invention

The invention aims to provide a preparation method for preparing a concrete plasticity-maintaining agent by using acid-washing phosphated waste residues, which overcomes the defects of the prior art, fully utilizes acid-washing phosphated waste residue resources, and is matched with iron tailings powder and sodium gluconate to produce the concrete plasticity-maintaining agent, so that the hydration speed of concrete slurry is slowed, the hydration hardening process and time are prolonged, the slump loss is reduced, and the slump maintaining performance of concrete is met.

In order to realize the purpose, the invention is realized by adopting the following technical scheme:

a preparation method for preparing a concrete plastic-retaining agent by using acid-washing phosphated waste residues is characterized by comprising the following components in parts by weight: 70-70.5 parts of iron phosphate waste residues, 29-29.66 parts of iron tailing powder and 0.34-1 part of sodium gluconate.

The iron phosphate waste residue is obtained from a steel rolling enterprise adopting a phosphate rust removal process, wherein the iron phosphate waste residue comprises the following chemical components in percentage by mass: h₂PO₄ 5～9.5％、SC(NH₂)₂ 0.1～0.5％、FePO₄·2H₂O 90～94.5％。

The iron tailing powder is taken from washed fine sand type iron tailings, wherein the chemical components in percentage by mass are as follows: SiO 2₂68.68％、CaO 5.25％、MgO 5.57％、Fe₂O₃ 15.13％、Al₂O₃2.97%, the balance 2.4% being inevitable impurities, the ignition loss being 1.12%.

The sodium gluconate is of industrial purity.

A preparation method for preparing a concrete plastic-retaining agent by using acid-washing phosphated waste residues is characterized in that the preparation process comprises homogenizing, mixing, activating, drying and metering and packaging, and specifically comprises the following steps:

1) homogenizing and mixing, namely mixing the iron phosphate waste residues, the iron tailing powder and the sodium gluconate according to the proportion, and continuously homogenizing and stirring the mixture by using an air-mechanical composite mixer at the linear speed of 4000-6000 mm/min to obtain a mixture with the homogenizing coefficient of 1-1.8;

2) activity deviceDrying, namely feeding the mixture into an activation drying mill with an activation ring and an activation lining plate, and heating to 60-85 ℃ by self friction of the mixture to ensure that thiourea and phosphoric acid in the mixture continue to react with Fe in the waste residue₂O₃Mixing to generate iron phosphate, removing thiourea and phosphoric acid, and pressing and grinding into a storage bin through negative pressure after the activated powder is qualified in granularity;

3) and (4) metering and packaging, namely, after the concrete is metered by a bucket scale, automatically packaging into bags by a rotary packaging machine to obtain the finished product of the concrete plasticity-maintaining agent.

The density of the finished product of the concrete plastic retaining agent is 1.25-1.63 g/cm3, and the screen residue of a square-hole sieve with the granularity of 0.08mm is less than 10%; initial setting time difference is +60 to +120min, the compressive strength ratio is 95 percent in 7 days, the compressive strength ratio is 120 percent in 28 days, and the softening coefficient is 0.55.

The addition amount of the finished product of the concrete plastic retaining agent is that 14-22 kg of the plastic retaining agent is directly added into each ton of concrete in the common pumping agent compounding, and is 3.5-5.5% of the dosage of the cementing material.

The addition amount of the concrete plastic retaining agent finished product is 5-5.5% of the dosage of the cementing material in the range of the environmental temperature of more than 20-35 ℃; the addition amount is 3.5-4.0% of the dosage of the cementing material in the range of the environmental temperature of 10-20 ℃.

Compared with the prior art, the invention has the beneficial effects that: 1) the produced acid-washing phosphatization waste residue plastic-retaining agent product has certain advantages of impermeability, condensation and working performance when applied to C30 concrete, so that the hydration speed of concrete slurry is reduced, the hydration hardening process and time are prolonged, the slump loss is slowed, and the cost is correspondingly reduced. 2) By researching the factors such as the mixing amount, the compressive strength, the setting time, the stability and the like of the acid pickling phosphorization waste residue, when the mixing amount is 4.5-5%, the compressive strength reaches 35.8-36.5 MPa; the static setting time is prolonged to 120min, the stability is qualified, and the slump loss of the concrete is 25-30 mm after 2 hours, so that the slump retention performance of the concrete is met.

Drawings

FIG. 1 is an XRD pattern of a raw material for iron phosphate slag in example 1 of the present invention.

FIG. 2 is an XRD spectrum of the cement gelling material doped with iron phosphate slag for 28 days in example 1 of the present invention.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example 1

0.34kg of sodium gluconate is added before the activation, drying and grinding; 29.66kg of iron tailing powder and 70kg of iron phosphate waste residue are subjected to physical activation and continuous grinding, homogenized and warehoused, metered and packaged to prepare the concrete plastic-retaining agent product. Taking C30 as an example, the addition amount of the concrete plasticity-maintaining agent product is 3.5 percent of the cementing material.

Example 2

Metering and adding 0.5kg of sodium gluconate before drying and grinding; 29.5kg of iron tailing powder and 70kg of iron phosphate slag are subjected to physical activation and continuous grinding, homogenized and warehoused, measured and packaged to obtain the concrete plastic-retaining agent product. Taking C30 as an example, the addition amount of the concrete plasticity-maintaining agent product is 4.0 percent of the cementing material.

Example 3

Metering and adding 0.66kg of sodium gluconate before drying and grinding; 29.34kg of iron tailing powder and 70kg of iron phosphate waste residue are subjected to physical activation and continuous grinding, homogenized and warehoused, metered and packaged to obtain the concrete plasticity-maintaining agent product. Taking C30 as an example, the addition amount of the concrete plasticity-maintaining agent product is 4.5 percent of the cementing material.

Example 4

Metering and adding 0.83kg of sodium gluconate before drying and grinding; 29.17kg of tailing powder and 70kg of iron phosphate slag are subjected to physical activation and continuous grinding, homogenized and warehoused, metered and packaged to prepare the concrete plastic-retaining agent product. Taking C30 as an example, the addition amount of the concrete plasticity-maintaining agent product is 5.0 percent of the cementing material.

Example 5

Metering and adding 1kg of sodium gluconate before drying and grinding; 29kg of iron tailing powder and 70kg of iron phosphate slag are subjected to physical activation and continuous grinding, homogenized and warehoused, metered and packaged to prepare the concrete plastic retention agent product. Taking C30 as an example, concrete

The addition amount of the plastic retention agent product is 5.5 percent of the gelled material.

In the above embodiment, the iron phosphate waste residue is obtained from a steel rolling enterprise adopting a phosphate rust removal process, wherein the iron phosphate waste residue comprises the following chemical components in percentage by mass: h₂PO₄ 5～9.5％、SC(NH₂)₂ 0.1～0.5％、FePO₄·2H₂And O90-94.5%. The iron tailing powder is taken from washed fine sand type iron tailings, wherein the chemical components in percentage by mass are as follows: SiO 2₂ 68.68％、CaO 5.25％、MgO 5.57％、Fe₂O₃ 15.13％、Al₂O₃2.97%, the balance 2.4% being inevitable impurities, the ignition loss being 1.12%. The sodium gluconate is of industrial purity.

The preparation process of the concrete plasticity-maintaining agent comprises the following steps: 1) mixing iron phosphate waste residues, iron tailing powder and sodium gluconate according to the proportion, and continuously homogenizing and stirring by using a pneumatic mechanical composite mixer at the linear speed of 4500-5500 mm/min to obtain a mixture with the homogenization coefficient of 1.2-1.6; 2) activating and drying, namely feeding the mixture into an activating and drying mill with an activating ring and an activating lining plate, and heating to 65-80 ℃ by self friction of the mixture so that thiourea and phosphoric acid in the mixture continue to react with Fe in the waste residue₂O₃Mixing to generate iron phosphate, removing thiourea and phosphoric acid, and pressing and grinding into a storage bin through negative pressure after the activated powder is qualified in granularity; 3) and (4) metering and packaging, namely, after the concrete is metered by a bucket scale, automatically packaging into bags by a rotary packaging machine to obtain the finished product of the concrete plasticity-maintaining agent.

Comparative example 1

Taking C30 concrete as an example, a naphthalene sodium lignosulfonate retarder is added, and the addition amount of the retarder is 1.0% of the cementing material.

Comparative example 2

Taking C30 concrete as an example, a sodium humate retarder is added, and the addition amount of the sodium humate retarder is 1.4% of the cementing material.

Comparative example 3

Taking C30 concrete as an example, calcium lignosulfonate retarder is added, and the addition amount of the calcium lignosulfonate retarder is 0.3% of the cementing material.

Comparative example 4

Taking C30 concrete as an example, a polycarboxylic acid retarder is added, and the addition amount of the polycarboxylic acid retarder is 2.8% of the cementing material.

Test procedure for concrete performance in examples and comparative examples tests for slump and strength in concrete were carried out according to the national standard GB/T14902-2012 test standard for examples 1-5 and comparative examples 1-4.

Slump and strength changes in C30 concrete using the above 1-5 examples of the present invention are shown in Table 1 below

TABLE 1

Example 2	4.0	2.8	220	210	190	--	--	25.5	35.1
										Example 3	4.5	2.8	220	220	215	200	195	24.0	35.8
Example 4	5.0	2.8	220	215	210	195	190	22.9	36.5
										Example 5	5.5	2.8	220	210	200	195	190	26.4	40.5

The parameters of comparative examples 1-4 are in table 2.

TABLE 2

Referring to fig. 1 and 2, XRD patterns of the iron phosphate slag raw material in example 1 of the present invention are shown, and fig. 1 demonstrates that iron phosphate with two crystal waters is present in the raw material. FIG. 2 is an XRD pattern of 28 days after iron phosphate slag was added to cement in accordance with example 1 of the present invention, and when 5% of the iron phosphate slag was added to the cement, it was generally accepted by the researchers that the reaction of the raw material of iron phosphate slag with cement did not produce calcium phosphate, and by finding out the reactant in the XRD pattern, it was demonstrated that iron phosphate substances were present and produced

The effect of slowing down the hydration speed of the concrete slurry is achieved, the hydration hardening process and time are prolonged, the slump loss is slowed down, the concrete slurry is recycled as waste resources, and the cost of the concrete can be reduced by 25-40%.

The above embodiments are merely specific examples selected for illustrating the objects, technical solutions and advantages of the present invention in detail, and should not be construed as limiting the scope of the present invention, and various modifications, equivalent substitutions and improvements can be made without departing from the spirit and principle of the present invention.