CN113185155B - Alkali-activated high-doping-amount copper smelting solid waste cement and preparation method thereof - Google Patents

Abstract

The invention belongs to the field of green disposal and resource utilization of solid wastes, and particularly discloses alkali-activated high-doping-amount copper smelting solid waste cement and a preparation method thereof. The raw materials adopted by the method comprise copper water quenching slag, copper smelting flue dust, desulfurized gypsum, fly ash, cement and an alkali activator, wherein the addition amount of the alkali activator accounts for 3-8% of the total weight of the rest materials. The preparation method is simple and easy to operate, alkali-activated cement with stable performance, good antibacterial performance and high stability of heavy metal elements can be obtained only by grinding and other procedures in the preparation process, and the prepared copper smelting solid waste cement can be widely applied to the fields of building engineering, road engineering and the like. The invention can realize the synergy, green disposal and resource utilization of the copper smelting solid waste, and has simple process and small environmental burden.

Description

Alkali-activated high-doping-amount copper smelting solid waste cement and preparation method thereof

Technical Field

The invention belongs to the field of green disposal and resource utilization of solid wastes, and particularly discloses alkali-activated high-doping-amount copper smelting solid waste cement and a preparation method thereof.

Background

The cement is one of the most important artificial building materials, is a basic raw material of national economy, and plays an important role in economic construction. Since the nineties of the last century, the cement yield of China is in the first place of the world for 27 years. In 2020, the cumulative cement yield in China is 23.77 hundred million tons, and the ratio is increased by 1.6 percent. Cement production is roughly divided into five processes: the method comprises the following steps of raw material mining, raw material preparation (grinding), clinker calcining, cement preparation (grinding) and cement loading, wherein the most key step is three stages of raw material preparation, clinker calcining and cement grinding, and the three stages are commonly called 'two-grinding and one-burning'. The cement industry is a high-energy-consumption and high-emission industry, and uses CO ₂ Emission of CO, for example, from cement industry ₂ Occupies CO of the whole world ₂ About 7% of the total discharge amount. Therefore, the development of the novel green cement-based material can not only reduce the resource and energy consumption, but also reduce the environmental pollution, and has remarkable social, economic and environmental benefits.

Copper is an indispensable resource in the development of human society, and China is the largest copper consumer country in the world. The yields of refined copper and copper materials in China are 1003 ten thousand tons (7.4 percent of the same ratio increase) and 2046 ten thousand tons (0.9 percent of the same ratio increase) respectively in 2020. The enormous copper production also comes with an incredible amount of copper-containing solid waste, mainly comprising: copper smelting slag, copper smelting flue dust and the like. At present, a large amount of copper-containing solid wastes are discarded and stockpiled, so that not only is the resource waste caused, but also the ecological environment safety is seriously threatened. Because cement has the advantages of wide application field, large consumption and the like, the preparation of the cement-based cementing material by using copper smelting solid wastes becomes a research hotspot.

Chinese patent 201811524497.1 discloses a copper slag portland cement material and a preparation method thereof. The method discloses a copper slag portland cement material which comprises the following components in percentage by weight: 5-15% of copper slag, 5-15% of slag, 2-6% of calcium hydroxide and the balance of cement. The method has the advantages of simple preparation process, low cost and the like, however, the mixing amount of solid wastes in the cement is low (only about 30 percent at most). Chinese patent 201710340757.9 discloses a method for preparing portland cement from carbide slag and copper slag melt separation slag, which comprises the following steps: dewatering and drying the carbide slag outside the rotary kiln; mixing the copper slag molten slag, the sandstone and the carbide slag into a mixture; and extruding and grinding the mixture, calcining by adopting a dry grinding and dry burning process to obtain cement clinker, and mixing and grinding the cement clinker and the retarder to obtain the silicate cement. The method produces the cement clinker by replacing 100% of the carbide slag with limestone, and has the advantages of saving limestone resource, mining and the like. However, the method still requires high-temperature calcination, and the energy consumption and greenhouse gas emission are large. Chinese patent 201810568891.9 discloses a preparation method of a copper slag-based inorganic cementing material. The method utilizes the reaction of smelting copper slag and potassium dihydrogen phosphate to prepare the iron phosphate chemical bonding material with high strength and moderate solidification speed. The method has the characteristics of high strength of the prepared inorganic cementing material and the like, but the doping amount of copper slag in the composite cementing material is only about 30 percent.

At present, the following problems still exist in the preparation of slag cement by taking copper smelting slag as a raw material: firstly, the doping amount of copper smelting solid waste in cement is low; secondly, copper water-quenched slag with high activity is used as a raw material, so that the synergistic treatment of copper smelting solid waste cannot be realized; thirdly, the performance of the prepared cement material is poor. Therefore, the development of a technology for preparing a slag cement material with a large mixing amount by the cooperation of copper smelting solid waste is urgently needed.

Disclosure of Invention

The invention provides alkali-activated copper smelting solid waste cement with large doping amount and a preparation method thereof, aiming at the problems of low copper smelting solid waste doping amount, low strength of prepared slag cement, multiple use of high-activity materials, incapability of realizing copper smelting solid waste synergistic treatment and the like in the copper smelting solid waste treatment and slag cement preparation technology.

The invention is realized by the following technical scheme:

a preparation method of alkali-activated high-dosage copper smelting solid waste cement comprises the following steps:

(1) grinding: respectively grinding copper water quenching slag, copper smelting flue dust, desulfurized gypsum, fly ash and cement clinker to a certain fineness;

(2) preparing an alkali activator: grinding the alkali activator to a certain fineness;

(3) mixing: mixing the materials ground in the step (1) to obtain a copper smelting solid waste mixture; mixing the alkali-activating agent prepared in the step (2) into the copper smelting solid waste mixture according to a certain proportion, and uniformly mixing in a mixer to obtain alkali-activated copper smelting solid waste cement with large doping amount;

Wherein the copper smelting solid waste mixture comprises the following materials in percentage by weight: 30-55% of copper water quenching slag, 1-5% of copper smelting flue ash, 3-8% of desulfurized gypsum, 7-20% of fly ash and 20-45% of cement clinker.

Among the raw materials, the copper water-quenched slag and the fly ash have higher hydration activity, and the early strength, the antibacterial performance and the like of the cement material can be improved by adjusting the addition proportion and the exciting agent scheme (the type, the proportion, the addition amount and the like of the exciting agent). Meanwhile, the leaching of heavy metal elements can be effectively regulated and controlled by adjusting the proportion of the heavy metal elements; the copper smelting flue dust can reduce the void ratio of particle accumulation, and the addition amount of the copper smelting flue dust is adjusted to improve the strength of a cement material; the desulfurized gypsum can play roles in retarding coagulation, promoting hydration process, strengthening hardening strength of cement materials, controlling leaching of heavy metal elements and the like.

Furthermore, the copper water-quenched slag is solid waste obtained after water quenching treatment of copper smelting slag, and the copper water-quenched slag has good hydration activity; the copper smelting flue dust is smoke dust collected in a flue gas purification system in the copper smelting process. The copper smelting flue dust has weak hydration activity and high content of heavy metals (Cu, Zn, Pb and the like), but can reduce the porosity of particle accumulation and contribute to improving the strength of cement materials. The cement clinker meets the 42.5 strength grade requirement.

Further, in the step (1), the specific surface area of the ground copper water-quenched slag is more than or equal to 500m ² Kg, the specific surface area of the copper smelting flue ash after grinding is more than or equal to 500m ² Kg, the specific surface area of the desulfurized gypsum after grinding is more than or equal to 450m ² Kg, the specific surface area of pulverized coal ash is more than or equal to 430m ² Per kg; the specific surface area of the ground cement clinker is more than or equal to 400 m ² /kg。

The wear resistance of different materials is different, and the materials are independently ground and then mixed, so that the components in the mixture have expected fineness, and the treatment cost and the reactivity of the components are considered; by adjusting the particle size ratio of various materials, the void ratio of particle accumulation can be reduced, thereby being beneficial to improving the strength of the composite cementing material; the high specific surface area of the material is helpful for leaching heavy metal elements. However, a high specific surface area also contributes to an increase in the hydration activity of the material, which in turn leads to the formation of more high-strength cementitious materials with a better "coating" effect on heavy metals. Therefore, the fineness of each material is adjusted, and the leaching concentration of the heavy metal elements is favorably reduced.

Further, the alkali-activator includes potassium salt and sodium salt; the potassium salt comprises one or two of potassium hydroxide and potassium carbonate, and the sodium salt comprises one or two of sodium hydroxide and sodium carbonate;

The addition amount of the alkali-activator is 3-8% of the weight of the copper smelting solid waste mixture;

the mass percentage of potassium salt and sodium salt in the alkali activator is (0.4-1): 1

Further, the 3d flexural strength of the alkali-activated copper smelting solid waste cement with large doping amount is more than or equal to 3.6MPa, the 3d compressive strength is more than or equal to 15.8MPa, the 28d flexural strength is more than or equal to 6.7MPa, and the 28d compressive strength is more than or equal to 43.1 MPa;

the alkali-activated high-dosage copper smelting solid waste cement has the antibacterial activity grade according to JieKe republic of China national Standard (

724310: 1977) evaluated as grade 0 or grade 1;

the content of leachable Cu in the alkali-activated copper smelting solid waste cement with large doping amount is less than 0.5 mg/L; the content of leachable Pb is respectively less than 0.2 mg/L; the content of leachable Zn is less than 0.3mg/L respectively; the content of the leachable Ni is less than 0.2 mg/L.

The alkali-activated copper-doped solid waste cement is prepared by adopting the method, wherein the alkali-activated copper-doped solid waste cement is prepared by adopting copper water quenching slag, copper smelting flue dust, desulfurized gypsum, fly ash and cement clinker as raw materials and adding an alkali activator;

the 3d breaking strength of the alkali-activated copper smelting solid waste cement with large doping amount is more than or equal to 3.6MPa, the 3d compressive strength is more than or equal to 15.8MPa, the 28d breaking strength is more than or equal to 6.7MPa, and the 28d compressive strength is more than or equal to 43.1 MPa;

The alkali-activated antibacterial activity grade of the copper-doped solid waste cement is determined according to the national standard of the common country of Jack: (

724310: 1977) evaluated as grade 0 or grade 1;

the content of leachable Cu in the alkali-activated copper smelting solid waste cement with large doping amount is less than 0.5 mg/L; the content of leachable Pb is respectively less than 0.2 mg/L; the content of leachable Zn is less than 0.3mg/L respectively; the content of the leachable Ni is less than 0.2 mg/L.

The invention has the technical effects that:

(1) the method effectively promotes the hydration reaction of the active components and the cement in the copper smelting solid waste by adjusting the proportion and the granularity of various solid wastes and the composition and the addition amount of the alkali-activating agent, thereby improving the doping amount of the copper smelting solid waste in the copper smelting solid waste cement.

The copper water-quenched slag and the fly ash have higher hydration activity, and the early strength, the antibacterial performance and the like of the cement material can be improved by adjusting the addition proportion and the exciting agent scheme (the type, the proportion, the addition amount and the like of the exciting agent). Meanwhile, the leaching of heavy metal elements can be effectively regulated and controlled by adjusting the proportion of the heavy metal elements; the copper smelting flue dust can reduce the void ratio of particle accumulation, and the addition amount of the copper smelting flue dust is adjusted to improve the strength of a cement material; the desulfurized gypsum can play roles in retarding coagulation, promoting hydration process, strengthening hardening strength of cement materials, controlling leaching of heavy metal elements and the like. Therefore, the hydration reaction of the active components and the cement in the copper smelting solid waste can be effectively promoted by adjusting the proportion and the granularity of various solid wastes and the composition and the addition amount of the alkali-activating agent, so that the doping amount of the copper smelting solid waste is increased.

(2) The method disclosed by the invention utilizes the copper water quenching slag, the copper smelting flue ash and the like as main raw materials to prepare the copper smelting solid waste cement with a large mixing amount, so that the synergistic treatment of the copper smelting solid waste and other solid wastes is realized, and meanwhile, the stable treatment of heavy metal elements in the copper smelting solid waste is also realized. During the hydration process of cement and other active components, the heavy metals such as Cu, Pb, Zn, Ni and the like in the materials are coated by the gel phase. Therefore, the invention not only can realize the cooperative treatment of various solid wastes, but also can realize the stable treatment of heavy metal elements.

(3) The copper smelting slag solid waste cement prepared by the method has the advantages of high solid waste doping amount (55-70%), high strength (which can meet the related requirements of 42.5 strength cement), good antibacterial effect and good heavy metal (Cu, Pb, Zn and Ni) stabilization effect.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.

On the contrary, the invention is intended to cover alternatives, modifications, equivalents and alternatives which may be included within the spirit and scope of the invention as defined by the appended claims. Furthermore, in the following detailed description of the present invention, certain specific details are set forth in order to provide a better understanding of the present invention. It will be apparent to one skilled in the art that the present invention may be practiced without these specific details.

Example 1

Respectively grinding the copper water quenching slag, the copper smelting flue dust, the desulfurized gypsum, the fly ash and the cement clinker to the specific surface area of 500m ² /kg、500m ² /kg、450m ² /kg、430m ² /kg、400m ² In terms of/kg. Grinding sodium hydroxide and potassium hydroxide powder, and mixing the potassium salt and the sodium salt according to the mass percentage of 0.4: 1. And then, mixing the ground copper water quenching slag, copper smelting flue dust, desulfurized gypsum, fly ash and cement clinker to obtain a copper smelting solid waste mixture, wherein the weight percentages of the materials in the mixture are as follows: 30% of copper water quenching slag, 5% of copper smelting flue ash, 3% of desulfurized gypsum, 17% of fly ash and 45% of cement clinker. Adding an alkali activator into the copper smelting solid waste mixture, wherein the adding amount of the alkali activator is 3% of the weight of the copper smelting solid waste mixture. And uniformly mixing the copper smelting solid waste mixture added with the alkali activator in a mixer to obtain the alkali-activated copper smelting solid waste cement with large doping amount. Through the test: the 3d breaking strength of the prepared copper smelting solid waste cement is 5.9MPa, the 3d compressive strength is 24MPa, the 28d breaking strength is 11.6 MPa, and the 28d compressive strength is 63.5 MPa; according to the national standard of the Czech republic of China (

724310: 1977), the antibacterial activity grade of the prepared copper smelting solid waste cement is grade 1; the contents of the leachable Cu, Pb, Zn and Ni in the prepared copper smelting solid waste cement are respectively 0.02mg/L, 0.01mg/L and 0.02 mg/L.

Example 2

Respectively grinding copper water quenching slag, copper smelting flue dust, desulfurized gypsum, fly ash and cement clinker to the specific surface area of 520m ² /kg、510m ² /kg、480m ² /kg、450m ² /kg、420m ² (iv) kg. Grinding sodium hydroxide and potassium carbonate into powder, and mixing the potassium salt and the sodium salt according to the mass percentage of 0.5: 1. And then, mixing the ground copper water quenching slag, copper smelting flue dust, desulfurized gypsum, fly ash and cement clinker to obtain a copper smelting solid waste mixture, wherein the weight percentages of the materials in the mixture are as follows: 55% of copper water quenching slag, 3% of copper smelting flue ash, 5% of desulfurized gypsum, 10% of fly ash and 27% of cement clinker. Activating with alkaliThe hair agent is added into the copper smelting solid waste mixture, and the adding amount of the alkali exciting agent is 4 percent of the weight of the copper smelting solid waste mixture. And uniformly mixing the copper smelting solid waste mixture added with the alkali activator in a mixer to obtain the alkali-activated copper smelting solid waste cement with large doping amount. Through the test: the 3d flexural strength of the prepared copper smelting solid waste cement is 3.75MPa, the 3d compressive strength is 16.1MPa, the 28d flexural strength is 7.3MPa, and the 28d compressive strength is 45.2 MPa; according to the national standard of the Czech republic of China (

724310: 1977), the antibacterial activity grade of the prepared copper smelting solid waste cement is 0 grade; the contents of the leachable Cu, Pb, Zn and Ni in the prepared copper smelting solid waste cement are respectively 0.08mg/L, 0.03mg/L and 0.01 mg/L.

Example 3

Respectively grinding copper water quenching slag, copper smelting flue dust, desulfurized gypsum, fly ash and cement clinker to the specific surface area of 540m ² /kg、530m ² /kg、486m ² /kg、470m ² /kg、440m ² (iv) kg. Grinding potassium hydroxide and sodium carbonate into powder, and mixing the potassium salt and the sodium salt according to the mass percentage of 0.6: 1. And then, mixing the ground copper water quenching slag, copper smelting flue dust, desulfurized gypsum, fly ash and cement clinker to obtain a copper smelting solid waste mixture, wherein the weight percentages of the materials in the mixture are as follows: 40% of copper water quenching slag, 2% of copper smelting flue ash, 4% of desulfurized gypsum, 16% of fly ash and 38% of cement clinker. Adding an alkali activator into the copper smelting solid waste mixture, wherein the adding amount of the alkali activator is 6 percent of the weight of the copper smelting solid waste mixture. And uniformly mixing the copper smelting solid waste mixture added with the alkali activator in a mixer to obtain the alkali-activated copper smelting solid waste cement with large doping amount. After testing: the 3d rupture strength of the prepared copper smelting solid waste cement is 6.85MPa, the 3d compressive strength is 18.3MPa, the 28d rupture strength is 8.6MPa, and the 28d compressive strength is 51.7 MPa; according to the national standard of the Czech republic of China (

724310: 1977), the antibacterial activity grade of the prepared copper smelting solid waste cement is 0 grade;the contents of the leachable Cu, Pb, Zn and Ni in the prepared copper smelting solid waste cement are respectively 0.07mg/L, 0.02mg/L, 0.03mg/L and 0.03 mg/L.

Example 4

Respectively grinding the copper water quenching slag, the copper smelting flue dust, the desulfurized gypsum, the fly ash and the cement clinker to the specific surface area of 516m ² /kg、521m ² /kg、492m ² /kg、483m ² /kg、420m ² (iv) kg. Grinding potassium carbonate and sodium carbonate into powder, and mixing the potassium salt and the sodium salt according to the mass percentage of 0.7: 1. And then, mixing the ground copper water quenching slag, copper smelting flue dust, desulfurized gypsum, fly ash and cement clinker to obtain a copper smelting solid waste mixture, wherein the weight percentages of the materials in the mixture are as follows: 50% of copper water quenching slag, 4% of copper smelting flue ash, 5% of desulfurized gypsum, 10% of fly ash and 31% of cement clinker. Adding an alkali activator into the copper smelting solid waste mixture, wherein the adding amount of the alkali activator is 7.5 percent of the weight of the copper smelting solid waste mixture. And uniformly mixing the copper smelting solid waste mixture added with the alkali activator in a mixer to obtain the alkali-activated copper smelting solid waste cement with large doping amount. After testing: the 3d flexural strength of the prepared copper smelting solid waste cement is 5.85MPa, the 3d compressive strength is 19.3MPa, the 28d flexural strength is 8.1MPa, and the 28d compressive strength is 53.6 MPa; according to the national standard of the Czech republic of China (

724310: 1977), the antibacterial activity grade of the prepared copper smelting solid waste cement is 0 grade; the contents of the leachable Cu, Pb, Zn and Ni in the prepared copper smelting solid waste cement are respectively 0.04mg/L, 0.03mg/L, 0.02mg/L and 0.01 mg/L.

Example 5

Respectively grinding copper water quenching slag, copper smelting flue dust, desulfurized gypsum, fly ash and cement clinker to 530m of specific surface area ² /kg、535m ² /kg、500m ² /kg、490m ² /kg、430m ² (iv) kg. Grinding potassium carbonate, sodium carbonate and potassium hydroxide into powder, and mixing according to the weight ratio of 0.8:1 of potassium salt to sodium salt. Then, the ground copper water quenching slag, copper smelting flue dust, desulfurized gypsum, fly ash and cement clinker are mixed to obtain copper smeltingRefining a solid waste mixture, wherein the weight percentage of each material in the mixture is as follows: 35% of copper water quenching slag, 5% of copper smelting flue ash, 6% of desulfurized gypsum, 20% of fly ash and 34% of cement clinker. Adding an alkali activator into the copper smelting solid waste mixture, wherein the adding amount of the alkali activator is 4.3 percent of the weight of the copper smelting solid waste mixture. And uniformly mixing the copper smelting solid waste mixture added with the alkali activator in a mixer to obtain the alkali-activated copper smelting solid waste cement with large doping amount. Through the test: the 3d flexural strength of the prepared copper smelting solid waste cement is 6.35MPa, the 3d compressive strength is 17.2MPa, the 28d flexural strength is 9.3MPa, and the 28d compressive strength is 67.5 MPa; according to the national standard of the Czech republic of China (

724310: 1977), the antibacterial activity grade of the prepared copper smelting solid waste cement is 0 grade; the contents of the leachable Cu, Pb, Zn and Ni in the prepared copper smelting solid waste cement are respectively 0.02mg/L, 0.03mg/L and 0.01 mg/L.

Example 6

Respectively grinding the copper water quenching slag, the copper smelting flue dust, the desulfurized gypsum, the fly ash and the cement clinker to the specific surface area of 525m ² /kg、525m ² /kg、510m ² /kg、485m ² /kg、440m ² In terms of/kg. Grinding potassium carbonate, sodium carbonate, potassium hydroxide and sodium hydroxide into powder, and mixing according to the weight ratio of 0.7:1 of potassium salt to sodium salt. And then, mixing the ground copper water quenching slag, copper smelting flue dust, desulfurized gypsum, fly ash and cement clinker to obtain a copper smelting solid waste mixture, wherein the weight percentages of the materials in the mixture are as follows: 49% of copper water quenching slag, 1% of copper smelting flue ash, 5% of desulfurized gypsum, 15% of fly ash and 30% of cement clinker. Adding an alkali activator into the copper smelting solid waste mixture, wherein the adding amount of the alkali activator is 7.5 percent of the weight of the copper smelting solid waste mixture. And uniformly mixing the copper smelting solid waste mixture added with the alkali activator in a mixer to obtain the alkali-activated copper smelting solid waste cement with large doping amount. Through the test: the 3d rupture strength of the prepared copper smelting solid waste cement is 7.75MPa, the 3d compressive strength is 18.8MPa, the 28d rupture strength is 11.6MPa, and the 28d compressive strength is 65.9 MPa; according to the national standard of the Czech republic of China (

724310: 1977), the antibacterial activity grade of the prepared copper smelting solid waste cement is 0 grade; the contents of the leachable Cu, Pb, Zn and Ni in the prepared copper smelting solid waste cement are respectively 0.02mg/L, 0.01mg/L, 0.02mg/L and 0.01 mg/L.

Example 7

Respectively grinding the copper water quenching slag, the copper smelting flue dust, the desulfurized gypsum, the fly ash and the cement clinker to the specific surface area of 500m ² /kg、515m ² /kg、520m ² /kg、500m ² /kg、480m ² In terms of/kg. Grinding potassium carbonate, potassium hydroxide and sodium hydroxide powder, and mixing according to the weight ratio of potassium salt to sodium salt of 0.7: 1. And then, mixing the ground copper water quenching slag, copper smelting flue dust, desulfurized gypsum, fly ash and cement clinker to obtain a copper smelting solid waste mixture, wherein the weight percentages of the materials in the mixture are as follows: 48% of copper water quenching slag, 2% of copper smelting flue ash, 5% of desulfurized gypsum, 20% of fly ash and 25% of cement clinker. Adding an alkali activator into the copper smelting solid waste mixture, wherein the adding amount of the alkali activator is 6 percent of the weight of the copper smelting solid waste mixture. And uniformly mixing the copper smelting solid waste mixture added with the alkali activator in a mixer to obtain the alkali-activated copper smelting solid waste cement with large doping amount. Through the test: the 3d rupture strength of the prepared copper smelting solid waste cement is 9.15MPa, the 3d compressive strength is 24.3MPa, the 28d rupture strength is 28.2MPa, and the 28d compressive strength is 72.1 MPa; according to the national standard of the Czech republic of China (

724310: 1977), the antibacterial activity grade of the prepared copper smelting solid waste cement is 0 grade; the contents of the leachable Cu, Pb, Zn and Ni in the prepared copper smelting solid waste cement are respectively 0.01mg/L, 0.02mg/L and 0.01 mg/L.

Example 8

Respectively grinding the copper water quenching slag, the copper smelting flue dust, the desulfurized gypsum, the fly ash and the cement clinker to the specific surface area of 500m ² /kg、500m ² /kg、516m ² /kg、510m ² /kg、490m ² In terms of/kg. Mixing carbonic acidGrinding potassium, potassium hydroxide and sodium hydroxide powder, and mixing according to the weight ratio of 0.8:1 of potassium salt to sodium salt. And then, mixing the ground copper water quenching slag, copper smelting flue dust, desulfurized gypsum, fly ash and cement clinker to obtain a copper smelting solid waste mixture, wherein the weight percentages of the materials in the mixture are as follows: 50% of copper water quenching slag, 5% of copper smelting flue ash, 5% of desulfurized gypsum, 10% of fly ash and 30% of cement clinker. Adding an alkali activator into the copper smelting solid waste mixture, wherein the adding amount of the alkali activator is 8 percent of the weight of the copper smelting solid waste mixture. And uniformly mixing the copper smelting solid waste mixture added with the alkali activator in a mixer to obtain the alkali-activated copper smelting solid waste cement with large doping amount. Through the test: the 3d flexural strength of the prepared copper smelting solid waste cement is 5.15MPa, the 3d compressive strength is 19.6MPa, the 28d flexural strength is 9.9MPa, and the 28d compressive strength is 60.1 MPa; according to the national standard of the Czech republic of China (

724310: 1977), the antibacterial activity grade of the prepared copper smelting solid waste cement is grade 1; the contents of the leachable Cu, Pb, Zn and Ni in the prepared copper smelting solid waste cement are respectively 0.02mg/L, 0.02mg/L and 0.01 mg/L.

Example 9

Respectively grinding the copper water quenching slag, the copper smelting flue dust, the desulfurized gypsum, the fly ash and the cement clinker to the specific surface area of 500m ² /kg、500m ² /kg、450m ² /kg、430m ² /kg、400m ² In terms of/kg. Grinding potassium hydroxide and sodium hydroxide powder, and mixing according to the weight ratio of potassium salt to sodium salt of 0.5: 1. And then, mixing the ground copper water quenching slag, copper smelting flue dust, desulfurized gypsum, fly ash and cement clinker to obtain a copper smelting solid waste mixture, wherein the weight percentages of the materials in the mixture are as follows: 40% of copper water quenching slag, 3% of copper smelting flue ash, 5% of desulfurized gypsum, 7% of fly ash and 45% of cement clinker. Adding an alkali activator into the copper smelting solid waste mixture, wherein the adding amount of the alkali activator is 5% of the weight of the copper smelting solid waste mixture. And uniformly mixing the copper smelting solid waste mixture added with the alkali activator in a mixer to obtain the alkali-activated copper smelting solid waste cement with large doping amount. Through the test: prepared byThe 3d flexural strength of the copper smelting solid waste cement is 6.2MPa, the 3d compressive strength is 25MPa, the 28d flexural strength is 10.8MPa, and the 28d compressive strength is 58 MPa; according to the national standard of the Czech republic of China (

724310: 1977), the antibacterial activity grade of the prepared copper smelting solid waste cement is grade 1; the contents of the leachable Cu, Pb, Zn and Ni in the prepared copper smelting solid waste cement are respectively 0.02mg/L, 0.01mg/L and 0.01 mg/L.

Example 10

Respectively grinding the copper water quenching slag, the copper smelting flue dust, the desulfurized gypsum, the fly ash and the cement clinker to the specific surface area of 500m ² /kg、500m ² /kg、450m ² /kg、430m ² /kg、400m ² In terms of/kg. Grinding potassium hydroxide and sodium hydroxide powder, and mixing according to the weight ratio of potassium salt to sodium salt of 0.7: 1. And then, mixing the ground copper water quenching slag, copper smelting flue dust, desulfurized gypsum, fly ash and cement clinker to obtain a copper smelting solid waste mixture, wherein the weight percentages of the materials in the mixture are as follows: 49% of copper water quenching slag, 4% of copper smelting flue ash, 7% of desulfurized gypsum, 10% of fly ash and 30% of cement clinker. Adding an alkali activator into the copper smelting solid waste mixture, wherein the adding amount of the alkali activator is 6 percent of the weight of the copper smelting solid waste mixture. And uniformly mixing the copper smelting solid waste mixture added with the alkali activator in a mixer to obtain the alkali-activated copper smelting solid waste cement with large doping amount. Through the test: the 3d flexural strength of the prepared copper smelting solid waste cement is 6.8MPa, the 3d compressive strength is 25.8MPa, the 28d flexural strength is 12.3 MPa, and the 28d compressive strength is 65 MPa; according to the national standard of the Czech republic of China (

724310: 1977), the antibacterial activity grade of the prepared copper smelting solid waste cement is grade 1; the contents of the leachable Cu, Pb, Zn and Ni in the prepared copper smelting solid waste cement are respectively 0.01mg/L, 0.01mg/L and 0.01 mg/L.

Example 11

The copper water quenching slag, the copper smelting flue dust, the desulfurized gypsum, the fly ash and the cement are addedClinker, respectively grinding to specific surface area of 500m ² /kg、500m ² /kg、450m ² /kg、430m ² /kg、400m ² (iv) kg. Grinding potassium hydroxide and sodium hydroxide powder, and mixing according to the weight ratio of potassium salt to sodium salt of 0.5: 1. And then, mixing the ground copper water quenching slag, copper smelting flue dust, desulfurized gypsum, fly ash and cement clinker to obtain a copper smelting solid waste mixture, wherein the weight percentages of the materials in the mixture are as follows: 50% of copper water quenching slag, 2% of copper smelting flue ash, 8% of desulfurized gypsum, 20% of fly ash and 20% of cement clinker. Adding an alkali activator into the copper smelting solid waste mixture, wherein the adding amount of the alkali activator is 8 percent of the weight of the copper smelting solid waste mixture. And uniformly mixing the copper smelting solid waste mixture added with the alkali activator in a mixer to obtain the alkali-activated copper smelting solid waste cement with large doping amount. Through the test: the 3d flexural strength of the prepared copper smelting solid waste cement is 6.3MPa, the 3d compressive strength is 24.2MPa, the 28d flexural strength is 11.9 MPa, and the 28d compressive strength is 60.3 MPa; according to the national standard of the Czech republic of China (

724310: 1977), the antibacterial activity grade of the prepared copper smelting solid waste cement is 0 grade; the contents of the leachable Cu, Pb, Zn and Ni in the prepared copper smelting solid waste cement are respectively 0.02mg/L, 0.01mg/L and 0.02 mg/L.

Example 12

Respectively grinding copper water quenching slag, copper smelting flue dust, desulfurized gypsum, fly ash and cement clinker to the specific surface area of 520m ² /kg、510m ² /kg、480m ² /kg、450m ² /kg、420m ² In terms of/kg. Grinding sodium hydroxide and potassium carbonate powder, and mixing according to the weight ratio of 0.8:1 of potassium salt to sodium salt. And then, mixing the ground copper water quenching slag, copper smelting flue dust, desulfurized gypsum, fly ash and cement clinker to obtain a copper smelting solid waste mixture, wherein the weight percentages of the materials in the mixture are as follows: 30% of copper water quenching slag, 5% of copper smelting flue ash, 3% of desulfurized gypsum, 7% of fly ash and 30% of cement clinker. Adding an alkali activator into the copper smelting solid waste mixture, wherein the adding amount of the alkali activator is 3% of the weight of the copper smelting solid waste mixture. Will be added inThe copper smelting solid waste mixture of the alkali activator is uniformly mixed in a mixer to obtain the alkali-activated copper smelting solid waste cement with large mixing amount. Through the test: the 3d breaking strength of the prepared copper smelting solid waste cement is 3.9MPa, the 3d compressive strength is 18MPa, the 28d breaking strength is 7.6MPa, and the 28d compressive strength is 43.2 MPa; according to the national standard of the Czech republic of China (

724310: 1977), the antibacterial activity grade of the prepared copper smelting solid waste cement is 0 grade; the contents of the leachable Cu, Pb, Zn and Ni in the prepared copper smelting solid waste cement are respectively 0.01mg/L, 0.02mg/L and 0.02 mg/L.

Example 13

Respectively grinding copper water quenching slag, copper smelting flue dust, desulfurized gypsum, fly ash and cement clinker to the specific surface area of 520m ² /kg、510m ² /kg、480m ² /kg、450m ² /kg、420m ² In terms of/kg. Grinding potassium carbonate and sodium hydroxide powder, and mixing according to the weight ratio of potassium salt to sodium salt of 0.4: 1. And then, mixing the ground copper water quenching slag, copper smelting flue dust, desulfurized gypsum, fly ash and cement clinker to obtain a copper smelting solid waste mixture, wherein the weight percentages of the materials in the mixture are as follows: 45% of copper water quenching slag, 3% of copper smelting flue ash, 6% of desulfurized gypsum, 15% of fly ash and 35% of cement clinker. Adding an alkali activator into the copper smelting solid waste mixture, wherein the adding amount of the alkali activator is 6 percent of the weight of the copper smelting solid waste mixture. And uniformly mixing the copper smelting solid waste mixture added with the alkali activator in a mixer to obtain the alkali-activated copper smelting solid waste cement with large doping amount. Through the test: the 3d flexural strength of the prepared copper smelting solid waste cement is 4.2MPa, the 3d compressive strength is 18.6MPa, the 28d flexural strength is 7.9MPa, and the 28d compressive strength is 48.3 MPa; according to the national standard of the Czech republic of China (

724310: 1977), the antibacterial activity grade of the prepared copper smelting solid waste cement is 0 grade; the contents of the leachable Cu, Pb, Zn and Ni in the prepared copper smelting solid waste cement are respectively 0.03mg/L, 0.02mg/L, 0.01mg/L and 0.02 mg/L.

Example 14

Respectively grinding copper water quenching slag, copper smelting flue dust, desulfurized gypsum, fly ash and cement clinker to 520m of specific surface area ² /kg、510m ² /kg、480m ² /kg、450m ² /kg、420m ² In terms of/kg. Grinding potassium carbonate and sodium hydroxide powder, and mixing according to the weight ratio of potassium salt to sodium salt of 0.9: 1. And then, mixing the ground copper water quenching slag, copper smelting flue dust, desulfurized gypsum, fly ash and cement clinker to obtain a copper smelting solid waste mixture, wherein the weight percentages of the materials in the mixture are as follows: 50% of copper water quenching slag, 5% of copper smelting flue ash, 8% of desulfurized gypsum, 20% of fly ash and 27% of cement clinker. Adding an alkali activator into the copper smelting solid waste mixture, wherein the adding amount of the alkali activator is 8 percent of the weight of the copper smelting solid waste mixture. And uniformly mixing the copper smelting solid waste mixture added with the alkali activator in a mixer to obtain the alkali-activated copper smelting solid waste cement with large doping amount. Through the test: the 3d flexural strength of the prepared copper smelting solid waste cement is 4.3MPa, the 3d compressive strength is 19.2MPa, the 28d flexural strength is 8.2MPa, and the 28d compressive strength is 49.2 MPa; according to the national standard of the Czech republic of China (

724310: 1977), the antibacterial activity grade of the prepared copper smelting solid waste cement is 0 grade; the contents of the leachable Cu, Pb, Zn and Ni in the prepared copper smelting solid waste cement are respectively 0.01mg/L, 0.02mg/L, 0.01mg/L and 0.02 mg/L.

Example 15

Respectively grinding copper water quenching slag, copper smelting flue dust, desulfurized gypsum, fly ash and cement clinker to the specific surface area of 540m ² /kg、530m ² /kg、486m ² /kg、470m ² /kg、440m ² In terms of/kg. Grinding sodium carbonate and potassium hydroxide powder, and mixing according to the weight ratio of 0.8:1 of potassium salt to sodium salt. And then, mixing the ground copper water quenching slag, copper smelting flue dust, desulfurized gypsum, fly ash and cement clinker to obtain a copper smelting solid waste mixture, wherein the weight percentages of the materials in the mixture are as follows: 40% of copper water quenching slag, 5% of copper smelting flue ash, 3% of desulfurized gypsum, 7% of fly ash and cement clinker45 percent. Adding an alkali activator into the copper smelting solid waste mixture, wherein the adding amount of the alkali activator is 3% of the weight of the copper smelting solid waste mixture. And uniformly mixing the copper smelting solid waste mixture added with the alkali activator in a mixer to obtain the alkali-activated copper smelting solid waste cement with large doping amount. Through the test: the 3d flexural strength of the prepared copper smelting solid waste cement is 5.16MPa, the 3d compressive strength is 17.3MPa, the 28d flexural strength is 7.5MPa, and the 28d compressive strength is 50.6 MPa; according to the national standard of the Czech republic of China (

724310: 1977), the antibacterial activity grade of the prepared copper smelting solid waste cement is grade 1; the contents of the leachable Cu, Pb, Zn and Ni in the prepared copper smelting solid waste cement are respectively 0.02mg/L, 0.02mg/L and 0.01 mg/L.

Example 16

Respectively grinding copper water quenching slag, copper smelting flue dust, desulfurized gypsum, fly ash and cement clinker to the specific surface area of 540m ² /kg、530m ² /kg、486m ² /kg、470m ² /kg、440m ² In terms of/kg. Grinding sodium carbonate and potassium hydroxide powder, and mixing according to the weight ratio of 0.6:1 of potassium salt to sodium salt. And then, mixing the ground copper water quenching slag, copper smelting flue dust, desulfurized gypsum, fly ash and cement clinker to obtain a copper smelting solid waste mixture, wherein the weight percentages of the materials in the mixture are as follows: 50% of copper water quenching slag, 4% of copper smelting flue ash, 6% of desulfurized gypsum, 10% of fly ash and 30% of cement clinker. Adding an alkali activator into the copper smelting solid waste mixture, wherein the adding amount of the alkali activator is 5 percent of the weight of the copper smelting solid waste mixture. And uniformly mixing the copper smelting solid waste mixture added with the alkali activator in a mixer to obtain the alkali-activated copper smelting solid waste cement with large doping amount. Through the test: the 3d flexural strength of the prepared copper smelting solid waste cement is 6.75MPa, the 3d compressive strength is 18.4MPa, the 28d flexural strength is 8.7 MPa, and the 28d compressive strength is 52.6 MPa; according to the national standard of the Czech republic of China (

724310: 1977), antibacterial activity grade of the prepared copper smelting solid waste cementIs 0 grade; the contents of the leachable Cu, Pb, Zn and Ni in the prepared copper smelting solid waste cement are respectively 0.02mg/L, 0.01mg/L and 0.02 mg/L.

Example 17

Respectively grinding copper water quenching slag, copper smelting flue dust, desulfurized gypsum, fly ash and cement clinker to the specific surface area of 540m ² /kg、530m ² /kg、486m ² /kg、470m ² /kg、440m ² In terms of/kg. Grinding sodium carbonate and potassium hydroxide powder, and mixing according to the weight ratio of 0.5:1 of potassium salt to sodium salt. And then, mixing the ground copper water quenching slag, copper smelting flue dust, desulfurized gypsum, fly ash and cement clinker to obtain a copper smelting solid waste mixture, wherein the weight percentages of the materials in the mixture are as follows: 49% of copper water quenching slag, 3% of copper smelting flue ash, 8% of desulfurized gypsum, 20% of fly ash and 20% of cement clinker. Adding an alkali activator into the copper smelting solid waste mixture, wherein the adding amount of the alkali activator is 8 percent of the weight of the copper smelting solid waste mixture. And uniformly mixing the copper smelting solid waste mixture added with the alkali activator in a mixer to obtain the alkali-activated copper smelting solid waste cement with large doping amount. Through the test: the 3d flexural strength of the prepared copper smelting solid waste cement is 7.2MPa, the 3d compressive strength is 19.3MPa, the 28d flexural strength is 10.2 MPa, and the 28d compressive strength is 58.8 MPa; according to the national standard of the Czech republic of China (

724310: 1977), the antibacterial activity grade of the prepared copper smelting solid waste cement is 0 grade; the contents of the leachable Cu, Pb, Zn and Ni in the prepared copper smelting solid waste cement are respectively 0.02mg/L, 0.02mg/L and 0.01 mg/L.

Example 18

Respectively grinding the copper water quenching slag, the copper smelting flue dust, the desulfurized gypsum, the fly ash and the cement clinker to the specific surface area of 516m ² /kg、521m ² /kg、492m ² /kg、483m ² /kg、420m ² In terms of/kg. Grinding potassium carbonate and sodium carbonate powder, and mixing according to the weight ratio of 0.4:1 of potassium salt and sodium salt. Then, the ground copper water quenching slag, copper smelting flue dust, desulfurized gypsum, fly ash and cement clinker are mixed to obtain copper smelting solid waste mixtureThe compound comprises the following materials in percentage by weight: 45% of copper water quenching slag, 5% of copper smelting flue ash, 3% of desulfurized gypsum, 7% of fly ash and 40% of cement clinker. Adding an alkali activator into the copper smelting solid waste mixture, wherein the adding amount of the alkali activator is 3% of the weight of the copper smelting solid waste mixture. And uniformly mixing the copper smelting solid waste mixture added with the alkali activator in a mixer to obtain the alkali-activated copper smelting solid waste cement with large doping amount. Through the test: the 3d flexural strength of the prepared copper smelting solid waste cement is 4.9MPa, the 3d compressive strength is 18.0MPa, the 28d flexural strength is 7.7MPa, and the 28d compressive strength is 50.3 MPa; according to the national standard of the Czech republic of China (

724310: 1977), the antibacterial activity grade of the prepared copper smelting solid waste cement is grade 1; the contents of the leachable Cu, Pb, Zn and Ni in the prepared copper smelting solid waste cement are respectively 0.01mg/L, 0.01mg/L and 0.01 mg/L.

Example 19

Respectively grinding the copper water quenching slag, the copper smelting flue dust, the desulfurized gypsum, the fly ash and the cement clinker to the specific surface area of 516m ² /kg、521m ² /kg、492m ² /kg、483m ² /kg、420m ² In terms of/kg. Grinding potassium carbonate and sodium carbonate powder, and mixing according to the weight ratio of 0.9:1 of potassium salt and sodium salt. And then, mixing the ground copper water quenching slag, copper smelting flue dust, desulfurized gypsum, fly ash and cement clinker to obtain a copper smelting solid waste mixture, wherein the weight percentages of the materials in the mixture are as follows: 40% of copper water quenching slag, 5% of copper smelting flue ash, 6% of desulfurized gypsum, 15% of fly ash and 34% of cement clinker. Adding an alkali activator into the copper smelting solid waste mixture, wherein the adding amount of the alkali activator is 5% of the weight of the copper smelting solid waste mixture. And uniformly mixing the copper smelting solid waste mixture added with the alkali activator in a mixer to obtain the alkali-activated copper smelting solid waste cement with large doping amount. Through the test: the 3d flexural strength of the prepared copper smelting solid waste cement is 5.6MPa, the 3d compressive strength is 18.5MPa, the 28d flexural strength is 7.6MPa, and the 28d compressive strength is 52.0 MPa; according to the national standard of the Czech republic of China (

724310: 1977), the antibacterial activity grade of the prepared copper smelting solid waste cement is 0 grade; the contents of the leachable Cu, Pb, Zn and Ni in the prepared copper smelting solid waste cement are respectively 0.02mg/L, 0.02mg/L and 0.02 mg/L.

Example 20

Respectively grinding the copper water quenching slag, the copper smelting flue dust, the desulfurized gypsum, the fly ash and the cement clinker to the specific surface area of 516m ² /kg、521m ² /kg、492m ² /kg、483m ² /kg、420m ² (iv) kg. Grinding potassium carbonate and sodium carbonate powder, and mixing according to the weight ratio of 0.7:1 of potassium salt and sodium salt. And then, mixing the ground copper water quenching slag, copper smelting flue dust, desulfurized gypsum, fly ash and cement clinker to obtain a copper smelting solid waste mixture, wherein the weight percentages of the materials in the mixture are as follows: 55% of copper water quenching slag, 2% of copper smelting flue ash, 8% of desulfurized gypsum, 10% of fly ash and 25% of cement clinker. Adding an alkali activator into the copper smelting solid waste mixture, wherein the adding amount of the alkali activator is 8 percent of the weight of the copper smelting solid waste mixture. And uniformly mixing the copper smelting solid waste mixture added with the alkali activator in a mixer to obtain the alkali-activated copper smelting solid waste cement with large doping amount. Through the test: the 3d flexural strength of the prepared copper smelting solid waste cement is 6.6MPa, the 3d compressive strength is 22.3MPa, the 28d flexural strength is 8.7MPa, and the 28d compressive strength is 58.8 MPa; according to the national standard of the Czech republic of China (

724310: 1977), the antibacterial activity grade of the prepared copper smelting solid waste cement is 0 grade; the contents of the leachable Cu, Pb, Zn and Ni in the prepared copper smelting solid waste cement are respectively 0.02mg/L, 0.01mg/L and 0.01 mg/L.

Example 21

Respectively grinding the copper water quenching slag, the copper smelting flue dust, the desulfurized gypsum, the fly ash and the cement clinker to the specific surface area of 530m ² /kg、535m ² /kg、500m ² /kg、490m ² /kg、430m ² In terms of/kg. Grinding potassium carbonate, sodium carbonate and potassium hydroxide into powder, and mixing with potassium salt and sodiumThe weight ratio of the salts was 0.6: 1. And then, mixing the ground copper water quenching slag, copper smelting flue dust, desulfurized gypsum, fly ash and cement clinker to obtain a copper smelting solid waste mixture, wherein the weight percentages of the materials in the mixture are as follows: 55% of copper water quenching slag, 5% of copper smelting flue ash, 3% of desulfurized gypsum, 7% of fly ash and 30% of cement clinker. Adding an alkali activator into the copper smelting solid waste mixture, wherein the adding amount of the alkali activator is 3% of the weight of the copper smelting solid waste mixture. And uniformly mixing the copper smelting solid waste mixture added with the alkali activator in a mixer to obtain the alkali-activated copper smelting solid waste cement with large doping amount. Through the test: the 3d flexural strength of the prepared copper smelting solid waste cement is 5.9MPa, the 3d compressive strength is 17.2MPa, the 28d flexural strength is 9.2 MPa, and the 28d compressive strength is 60.2 MPa; according to the national standard of the Czech republic of China (

724310: 1977), the antibacterial activity grade of the prepared copper smelting solid waste cement is grade 1; the contents of the leachable Cu, Pb, Zn and Ni in the prepared copper smelting solid waste cement are respectively 0.02mg/L, 0.02mg/L and 0.01 mg/L.

Example 22

Respectively grinding the copper water quenching slag, the copper smelting flue dust, the desulfurized gypsum, the fly ash and the cement clinker to the specific surface area of 530m ² /kg、535m ² /kg、500m ² /kg、490m ² /kg、430m ² In terms of/kg. Grinding potassium carbonate, sodium carbonate and potassium hydroxide into powder, and mixing the powder according to the weight ratio of 1:1 of potassium salt to sodium salt. And then, mixing the ground copper water quenching slag, copper smelting flue dust, desulfurized gypsum, fly ash and cement clinker to obtain a copper smelting solid waste mixture, wherein the weight percentages of the materials in the mixture are as follows: 46% of copper water quenching slag, 4% of copper smelting flue ash, 5% of desulfurized gypsum, 10% of fly ash and 40% of cement clinker. Adding an alkali activator into the copper smelting solid waste mixture, wherein the adding amount of the alkali activator is 6 percent of the weight of the copper smelting solid waste mixture. And uniformly mixing the copper smelting solid waste mixture added with the alkali activator in a mixer to obtain the alkali-activated copper smelting solid waste cement with large doping amount. Through the test: 3d breaking strength of the prepared copper smelting solid waste cement is 6.4MPa, and 3d breaking strength of the prepared copper smelting solid waste cement is 3dThe pressure intensity is 17.2MPa, the 28d flexural strength is 10.2MPa, and the 28d compressive strength is 62.6 MPa; according to the national standard of the Czech republic of China (

724310: 1977), the antibacterial activity grade of the prepared copper smelting solid waste cement is 0 grade; the contents of the leachable Cu, Pb, Zn and Ni in the prepared copper smelting solid waste cement are respectively 0.02mg/L, 0.01mg/L, 0.02mg/L and 0.01 mg/L.

Example 23

Respectively grinding the copper water quenching slag, the copper smelting flue dust, the desulfurized gypsum, the fly ash and the cement clinker to the specific surface area of 530m ² /kg、535m ² /kg、500m ² /kg、490m ² /kg、430m ² In terms of/kg. Grinding potassium carbonate, sodium carbonate and potassium hydroxide into powder, and mixing the powder according to the weight ratio of 1:1 of potassium salt to sodium salt. And then, mixing the ground copper water quenching slag, copper smelting flue dust, desulfurized gypsum, fly ash and cement clinker to obtain a copper smelting solid waste mixture, wherein the weight percentages of the materials in the mixture are as follows: 50% of copper water quenching slag, 3% of copper smelting flue ash, 8% of desulfurized gypsum, 15% of fly ash and 34% of cement clinker. Adding an alkali activator into the copper smelting solid waste mixture, wherein the adding amount of the alkali activator is 8 percent of the weight of the copper smelting solid waste mixture. And uniformly mixing the copper smelting solid waste mixture added with the alkali activator in a mixer to obtain the alkali-activated copper smelting solid waste cement with large doping amount. Through the test: the 3d breaking strength of the prepared copper smelting solid waste cement is 7.2MPa, the 3d compressive strength is 18.0MPa, the 28d breaking strength is 11.2MPa, and the 28d compressive strength is 69.2 MPa; according to the national standard of the Czech republic of China (

724310: 1977), the antibacterial activity grade of the prepared copper smelting solid waste cement is 0 grade; the contents of the leachable Cu, Pb, Zn and Ni in the prepared copper smelting solid waste cement are respectively 0.02mg/L, 0.01mg/L and 0.01 mg/L.

Example 24

Respectively grinding the copper water quenching slag, the copper smelting flue dust, the desulfurized gypsum, the fly ash and the cement clinker to the specific surface area of 525m ² /kg、525m ² /kg、510m ² /kg、485m ² /kg、440m ² (iv) kg. Grinding potassium carbonate, sodium carbonate, potassium hydroxide and sodium hydroxide into powder, and mixing according to the weight ratio of 0.9:1 of potassium salt to sodium salt. And then, mixing the ground copper water quenching slag, copper smelting flue dust, desulfurized gypsum, fly ash and cement clinker to obtain a copper smelting solid waste mixture, wherein the weight percentages of the materials in the mixture are as follows: 35% of copper water quenching slag, 5% of copper smelting flue ash, 5% of desulfurized gypsum, 20% of fly ash and 35% of cement clinker. Adding an alkali activator into the copper smelting solid waste mixture, wherein the adding amount of the alkali activator is 3% of the weight of the copper smelting solid waste mixture. And uniformly mixing the copper smelting solid waste mixture added with the alkali activator in a mixer to obtain the alkali-activated copper smelting solid waste cement with large doping amount. Through the test: the 3d flexural strength of the prepared copper smelting solid waste cement is 7.0MPa, the 3d compressive strength is 17.5MPa, the 28d flexural strength is 10.1MPa, and the 28d compressive strength is 52.9 MPa; according to the national standard of the Czech republic of China (

724310: 1977), the antibacterial activity grade of the prepared copper smelting solid waste cement is grade 1; the contents of the leachable Cu, Pb, Zn and Ni in the prepared copper smelting solid waste cement are respectively 0.02mg/L, 0.01mg/L and 0.01 mg/L.

Example 25

Respectively grinding the copper water quenching slag, the copper smelting flue dust, the desulfurized gypsum, the fly ash and the cement clinker to the specific surface area of 525m ² /kg、525m ² /kg、510m ² /kg、485m ² /kg、440m ² In terms of/kg. Grinding potassium carbonate, sodium carbonate, potassium hydroxide and sodium hydroxide into powder, and mixing according to the weight ratio of 0.8:1 of potassium salt to sodium salt. And then, mixing the ground copper water quenching slag, copper smelting flue dust, desulfurized gypsum, fly ash and cement clinker to obtain a copper smelting solid waste mixture, wherein the weight percentages of the materials in the mixture are as follows: 45% of copper water quenching slag, 2% of copper smelting flue ash, 8% of desulfurized gypsum, 10% of fly ash and 35% of cement clinker. Adding an alkali activator into the copper smelting solid waste mixture, wherein the adding amount of the alkali activator is the weight of the copper smelting solid waste mixture5 percent. And uniformly mixing the copper smelting solid waste mixture added with the alkali activator in a mixer to obtain the alkali-activated copper smelting solid waste cement with large doping amount. Through the test: the 3d rupture strength of the prepared copper smelting solid waste cement is 7.5MPa, the 3d compressive strength is 18.6MPa, the 28d rupture strength is 11.2MPa, and the 28d compressive strength is 65.1 MPa; according to the national standard of the Czech republic of China (

724310: 1977), the antibacterial activity grade of the prepared copper smelting solid waste cement is 0 grade; the contents of the leachable Cu, Pb, Zn and Ni in the prepared copper smelting solid waste cement are respectively 0.01mg/L, 0.01mg/L and 0.01 mg/L.

Example 26

Respectively grinding the copper water quenching slag, the copper smelting flue dust, the desulfurized gypsum, the fly ash and the cement clinker to the specific surface area of 525m ² /kg、525m ² /kg、510m ² /kg、485m ² /kg、440m ² In terms of/kg. Grinding potassium carbonate, sodium carbonate, potassium hydroxide and sodium hydroxide into powder, and mixing according to the weight ratio of 0.7:1 of potassium salt to sodium salt. And then, mixing the ground copper water quenching slag, copper smelting flue dust, desulfurized gypsum, fly ash and cement clinker to obtain a copper smelting solid waste mixture, wherein the weight percentages of the materials in the mixture are as follows: 55% of copper water quenching slag, 2% of copper smelting flue ash, 8% of desulfurized gypsum, 10% of fly ash and 25% of cement clinker. Adding an alkali activator into the copper smelting solid waste mixture, wherein the adding amount of the alkali activator is 8 percent of the weight of the copper smelting solid waste mixture. And uniformly mixing the copper smelting solid waste mixture added with the alkali activator in a mixer to obtain the alkali-activated copper smelting solid waste cement with large doping amount. Through the test: the 3d flexural strength of the prepared copper smelting solid waste cement is 8.3MPa, the 3d compressive strength is 20.2MPa, the 28d flexural strength is 14.2MPa, and the 28d compressive strength is 66.2 MPa; according to the national standard of the Czech republic of China (

724310: 1977), the antibacterial activity grade of the prepared copper smelting solid waste cement is 0 grade; the content of leached Cu, Pb, Zn and Ni in the prepared copper smelting solid waste cement is 0.01 mg/ml L、0.01mg/L、0.01mg/L、 0.01mg/L。

Example 27

Respectively grinding the copper water quenching slag, the copper smelting flue dust, the desulfurized gypsum, the fly ash and the cement clinker to the specific surface area of 500m ² /kg、515m ² /kg、520m ² /kg、500m ² /kg、480m ² In terms of/kg. Grinding potassium carbonate, potassium hydroxide and sodium hydroxide powder, and mixing according to the weight ratio of potassium salt to sodium salt of 0.6: 1. And then, mixing the ground copper water quenching slag, copper smelting flue dust, desulfurized gypsum, fly ash and cement clinker to obtain a copper smelting solid waste mixture, wherein the weight percentages of the materials in the mixture are as follows: 46% of copper water quenching slag, 4% of copper smelting flue ash, 3% of desulfurized gypsum, 7% of fly ash and 40% of cement clinker. Adding an alkali activator into the copper smelting solid waste mixture, wherein the adding amount of the alkali activator is 3% of the weight of the copper smelting solid waste mixture. And uniformly mixing the copper smelting solid waste mixture added with the alkali activator in a mixer to obtain the alkali-activated copper smelting solid waste cement with large doping amount. Through the test: the 3d flexural strength of the prepared copper smelting solid waste cement is 7.2MPa, the 3d compressive strength is 19.8MPa, the 28d flexural strength is 20.2MPa, and the 28d compressive strength is 58.8 MPa; according to the national standard of the Czech republic of China (

724310: 1977), the antibacterial activity grade of the prepared copper smelting solid waste cement is grade 1; the contents of the leachable Cu, Pb, Zn and Ni in the prepared copper smelting solid waste cement are respectively 0.02mg/L, 0.02mg/L and 0.01 mg/L.

Example 28

Respectively grinding the copper water quenching slag, the copper smelting flue dust, the desulfurized gypsum, the fly ash and the cement clinker to the specific surface area of 500m ² /kg、515m ² /kg、520m ² /kg、500m ² /kg、480m ² In terms of/kg. Grinding potassium carbonate, potassium hydroxide and sodium hydroxide powder, and mixing according to the weight ratio of potassium salt to sodium salt of 0.5: 1. And then, mixing the ground copper water quenching slag, copper smelting flue dust, desulfurized gypsum, fly ash and cement clinker to obtain a copper smelting solid waste mixture, wherein the weight percentages of the materials in the mixture are as follows: copper water quenching47% of slag, 3% of copper smelting flue ash, 6% of desulfurized gypsum, 10% of fly ash and 40% of cement clinker. Adding an alkali activator into the copper smelting solid waste mixture, wherein the adding amount of the alkali activator is 5% of the weight of the copper smelting solid waste mixture. And uniformly mixing the copper smelting solid waste mixture added with the alkali activator in a mixer to obtain the alkali-activated copper smelting solid waste cement with large doping amount. Through the test: the 3d flexural strength of the prepared copper smelting solid waste cement is 8.9MPa, the 3d compressive strength is 22.2MPa, the 28d flexural strength is 25.6MPa, and the 28d compressive strength is 65.2 MPa; according to the national standard of the Czech republic of China (

724310: 1977), the antibacterial activity grade of the prepared copper smelting solid waste cement is 0 grade; the contents of the leachable Cu, Pb, Zn and Ni in the prepared copper smelting solid waste cement are respectively 0.01mg/L, 0.01mg/L and 0.01 mg/L.

Example 29

Respectively grinding the copper water quenching slag, the copper smelting flue dust, the desulfurized gypsum, the fly ash and the cement clinker to the specific surface area of 500m ² /kg、515m ² /kg、520m ² /kg、500m ² /kg、480m ² In terms of/kg. Grinding potassium carbonate, potassium hydroxide and sodium hydroxide powder, and mixing according to the weight ratio of potassium salt to sodium salt of 0.6: 1. And then, mixing the ground copper water quenching slag, copper smelting flue dust, desulfurized gypsum, fly ash and cement clinker to obtain a copper smelting solid waste mixture, wherein the weight percentages of the materials in the mixture are as follows: 49% of copper water quenching slag, 1% of copper smelting flue ash, 8% of desulfurized gypsum, 15% of fly ash and 27% of cement clinker. Adding an alkali activator into the copper smelting solid waste mixture, wherein the adding amount of the alkali activator is 8 percent of the weight of the copper smelting solid waste mixture. And uniformly mixing the copper smelting solid waste mixture added with the alkali activator in a mixer to obtain the alkali-activated copper smelting solid waste cement with large doping amount. Through the test: the 3d rupture strength of the prepared copper smelting solid waste cement is 9.2MPa, the 3d compressive strength is 28.0MPa, the 28d rupture strength is 30.1MPa, and the 28d compressive strength is 68.2 MPa; according to the national standard of the Czech republic of China (

724310: 1977), the antibacterial activity grade of the prepared copper smelting solid waste cement is 0 grade; the contents of the leachable Cu, Pb, Zn and Ni in the prepared copper smelting solid waste cement are respectively 0.02mg/L, 0.02mg/L and 0.01 mg/L.

Example 30

Respectively grinding the copper water quenching slag, the copper smelting flue dust, the desulfurized gypsum, the fly ash and the cement clinker to the specific surface area of 500m ² /kg、500m ² /kg、516m ² /kg、510m ² /kg、490m ² In terms of/kg. Grinding potassium carbonate, potassium hydroxide and sodium hydroxide into powder, and mixing according to the weight ratio of potassium salt to sodium salt of 0.8: 1. And then, mixing the ground copper water quenching slag, copper smelting flue dust, desulfurized gypsum, fly ash and cement clinker to obtain a copper smelting solid waste mixture, wherein the weight percentages of the materials in the mixture are as follows: 40% of copper water quenching slag, 5% of copper smelting flue ash, 3% of desulfurized gypsum, 7% of fly ash and 45% of cement clinker. Adding an alkali activator into the copper smelting solid waste mixture, wherein the adding amount of the alkali activator is 3% of the weight of the copper smelting solid waste mixture. And uniformly mixing the copper smelting solid waste mixture added with the alkali activator in a mixer to obtain the alkali-activated copper smelting solid waste cement with large doping amount. Through the test: the 3d flexural strength of the prepared copper smelting solid waste cement is 4.9MPa, the 3d compressive strength is 18.2MPa, the 28d flexural strength is 8.2MPa, and the 28d compressive strength is 53.2 MPa; according to the national standard of the Czech republic of China (

724310: 1977), the antibacterial activity grade of the prepared copper smelting solid waste cement is grade 1; the contents of the leachable Cu, Pb, Zn and Ni in the prepared copper smelting solid waste cement are respectively 0.02mg/L, 0.02mg/L and 0.01 mg/L.

Example 31

Respectively grinding the copper water quenching slag, the copper smelting flue dust, the desulfurized gypsum, the fly ash and the cement clinker to the specific surface area of 500m ² /kg、500m ² /kg、516m ² /kg、510m ² /kg、490m ² In terms of/kg. Grinding potassium carbonate, potassium hydroxide and sodium hydroxide into powder according to the weight ratio of potassium salt to sodium salt of 0.71, mixing. And then, mixing the ground copper water quenching slag, copper smelting flue dust, desulfurized gypsum, fly ash and cement clinker to obtain a copper smelting solid waste mixture, wherein the weight percentages of the materials in the mixture are as follows: 48% of copper water quenching slag, 2% of copper smelting flue ash, 6% of desulfurized gypsum, 15% of fly ash and 29% of cement clinker. Adding an alkali activator into the copper smelting solid waste mixture, wherein the adding amount of the alkali activator is 5% of the weight of the copper smelting solid waste mixture. And uniformly mixing the copper smelting solid waste mixture added with the alkali activator in a mixer to obtain the alkali-activated copper smelting solid waste cement with large doping amount. Through the test: the 3d flexural strength of the prepared copper smelting solid waste cement is 4.8MPa, the 3d compressive strength is 18.5MPa, the 28d flexural strength is 9.2MPa, and the 28d compressive strength is 58.8 MPa; according to the national standard of the Czech republic of China (

724310: 1977), the antibacterial activity grade of the prepared copper smelting solid waste cement is 0 grade; the contents of the leachable Cu, Pb, Zn and Ni in the prepared copper smelting solid waste cement are respectively 0.02mg/L, 0.01mg/L and 0.01 mg/L.

Example 32

Respectively grinding the copper water quenching slag, the copper smelting flue dust, the desulfurized gypsum, the fly ash and the cement clinker to the specific surface area of 500m ² /kg、500m ² /kg、516m ² /kg、510m ² /kg、490m ² In terms of/kg. Grinding potassium carbonate, potassium hydroxide and sodium hydroxide powder, and mixing according to the weight ratio of potassium salt to sodium salt of 0.6: 1. And then, mixing the ground copper water quenching slag, copper smelting flue dust, desulfurized gypsum, fly ash and cement clinker to obtain a copper smelting solid waste mixture, wherein the weight percentages of the materials in the mixture are as follows: 55% of copper water quenching slag, 4% of copper smelting flue ash, 8% of desulfurized gypsum, 11% of fly ash and 22% of cement clinker. Adding an alkali activator into the copper smelting solid waste mixture, wherein the adding amount of the alkali activator is 7 percent of the weight of the copper smelting solid waste mixture. And uniformly mixing the copper smelting solid waste mixture added with the alkali activator in a mixer to obtain the alkali-activated copper smelting solid waste cement with large doping amount. Through the test: 3d breaking strength of 5.3MPa and 3d compressive strength of the prepared copper smelting solid waste cement are 21.2MPa, 28d flexural strength of 12.2MPa and 28d compressive strength of 62 MPa; according to the national standard of the Czech republic of China (

724310: 1977), the antibacterial activity grade of the prepared copper smelting solid waste cement is 0 grade; the contents of the leachable Cu, Pb, Zn and Ni in the prepared copper smelting solid waste cement are respectively 0.01mg/L, 0.01mg/L and 0.01 mg/L.

The preparation method is simple and easy to operate, alkali-activated cement with stable performance, good antibacterial performance and high stability of heavy metal elements can be obtained only by grinding and other procedures in the preparation process, and the prepared copper smelting solid waste cement can be widely applied to the fields of building engineering, road engineering and the like. The method disclosed by the invention can realize the synergy, green treatment and resource utilization of the copper smelting solid waste, and is simple in process and small in environmental burden.

Claims (3)

1. A preparation method of alkali-activated high-doping-amount copper smelting solid waste cement is characterized by comprising the following steps:

(1) grinding: respectively grinding copper water quenching slag, copper smelting flue dust, desulfurized gypsum, fly ash and cement clinker to a certain fineness;

(2) preparing an alkali activator: grinding the alkali activator to a certain fineness;

(3) mixing: mixing the materials ground in the step (1) to obtain a copper smelting solid waste mixture; then mixing the alkali-activating agent prepared in the step (2) into the copper smelting solid waste mixture according to a certain proportion, and uniformly mixing to obtain alkali-activated copper smelting solid waste cement with a large doping amount;

wherein the copper smelting solid waste mixture comprises the following materials in percentage by weight: 30-55% of copper water quenching slag, 1-5% of copper smelting flue ash, 3-8% of desulfurized gypsum, 7-20% of fly ash and 20-45% of cement clinker;

The copper water quenching slag is solid waste obtained after water quenching treatment of copper smelting slag; the copper smelting flue dust is smoke dust collected in a flue gas purification system in the copper smelting process; the cement clinker meets the requirement of 42.5 strength grade;

in the step (1), the specific surface area of the ground copper water-quenched slag is more than or equal to 500 m ² Kg, the specific surface area of the copper smelting flue ash after grinding is more than or equal to 500 m ² Kg, the specific surface area of the desulfurized gypsum after grinding is more than or equal to 450 m ² Kg, the specific surface area of pulverized coal ash is more than or equal to 430 m ² Per kg; the specific surface area of the ground cement clinker is more than or equal to 400 m ² /kg；

The 3d breaking strength of the alkali-activated copper smelting solid waste cement with large doping amount is more than or equal to 3.6 MPa, the 3d compressive strength is more than or equal to 15.8 MPa, the 28d breaking strength is more than or equal to 6.7 MPa, and the 28d compressive strength is more than or equal to 43.1 MPa;

the antibacterial activity grade of the alkali-activated copper-doped solid waste cement is evaluated to be 0 grade or 1 grade according to the national standard Č SN 724310: 1977 of the Rickettsia;

the content of leachable Cu in the alkali-activated copper smelting solid waste cement with large doping amount is less than 0.5 mg/L; the content of leachable Pb is respectively less than 0.2 mg/L; the content of leachable Zn is less than 0.3 mg/L respectively; the content of the leachable Ni is less than 0.2 mg/L.

2. The method for preparing the alkali-activated copper smelting solid waste cement with large doping amount according to claim 1, wherein the alkali activator comprises potassium salt and sodium salt; the potassium salt comprises one or two of potassium hydroxide and potassium carbonate, and the sodium salt comprises one or two of sodium hydroxide and sodium carbonate;

The addition amount of the alkali-activator is 3-8% of the weight of the copper smelting solid waste mixture;

the mass percentage of potassium salt and sodium salt in the alkali activator is (0.4-1): 1.

3. The alkali-activated copper-doped solid waste cement is prepared by the method of claim 1 or 2, and is characterized in that the alkali-activated copper-doped solid waste cement is prepared by taking copper water quenching slag, copper smelting flue ash, desulfurized gypsum, fly ash and cement clinker as raw materials and adding an alkali activator;

the 3d breaking strength of the alkali-activated copper smelting solid waste cement with large doping amount is more than or equal to 3.6 MPa, the 3d compressive strength is more than or equal to 15.8 MPa, the 28d breaking strength is more than or equal to 6.7 MPa, and the 28d compressive strength is more than or equal to 43.1 MPa;

the antibacterial activity grade of the alkali-activated copper-doped solid waste cement is evaluated to be 0 grade or 1 grade according to the national standard Č SN 724310: 1977 of the Rickettsia;

the content of leachable Cu in the alkali-activated copper smelting solid waste cement with large doping amount is less than 0.5 mg/L; the content of leachable Pb is respectively less than 0.2 mg/L; the content of leachable Zn is less than 0.3 mg/L respectively; the content of the leachable Ni is less than 0.2 mg/L.