CN111573946B - Comprehensive utilization method of granite cutting waste liquid - Google Patents

Abstract

The invention discloses a comprehensive utilization method for stone cutting waste liquid, comprising the following steps: (1) adding low surface energy substances to the stone cutting waste liquid; (2) for gypsum, lime and other waste liquids, adopting a precipitation process to separate the Large particle waste residue with low saturated resin content; for solutions that are difficult to precipitate and high in unsaturated resin content, wet-modified fillers for water-based architectural coatings. The beneficial effects of the invention are as follows: on the basis of analyzing the composition of the stone cutting fluid, a sedimentation tank is used to separate large particles of calcium carbonate in the stone waste liquid, and then the unsaturated resin and the small particles of calcium carbonate are separated by evaporation combined with membrane filtration. No flocculant is added in the separation process to achieve green separation; and according to the characteristics of the waste residue after separation, differentiated applications are used to improve the application effect of the waste residue and realize the high-value utilization of the slag.

Description

A kind of comprehensive utilization method of granite cutting waste liquid

technical field

The invention relates to the technical field of granite cutting waste liquid utilization, in particular to a comprehensive utilization method for granite cutting waste liquid.

Background technique

The artificial granite waste slag contains about 75% calcite, about 10% dolomite and about 15% unsaturated resin and impurities. The particle distribution in the waste slag is uneven (as shown in Table 1) and the content of toxic and harmful substances is lower than the national level. Building standards (as shown in Table 2). In recent years, a series of new technologies for resource utilization of stone waste have been developed, but most of them are aimed at the waste marble powder produced by natural stone processing. For example, Zheng Changji reported a flue gas desulfurization method based on waste marble powder to treat waste from waste; Liu Yanming and Du Gaoxiang used industrial waste acid to react with granite waste residue to prepare gypsum for building materials; Li Junwei et al. A method of modifying the ground waste rock powder with anionic fluorosurfactant, the product can be used as a filler for polymer materials; Zhang Jian et al. reported a method for producing lime from Nan'an waste marble powder. These studies provide new ideas and new methods for the resource utilization of natural stone heavy calcium waste residue, but these processes are all based on the powder after drying of artificial granite waste residue liquid as raw material.

Table 1 Cumulative particle size in artificial granite waste

Table 2 Analysis results of toxic and harmful substances in artificial granite waste residues

The surface of the artificial granite waste residue contains unsaturated polyester resin residue, and in order to effectively separate the small particles of the waste residue from water, the flocculant polyacrylamide (PAM) is added during the concentration of the waste stone slurry, resulting in organic matter (unsaturated) in the waste residue. The content of resin and PAM) is 4.66%. In addition, it is found that the content of unsaturated resin in the small particles in the waste residue is higher than that in the large particles. These polymer residues have caused great difficulties in the recycling of artificial granite heavy calcium waste residues. For example, the use of heavy calcium waste residues containing unsaturated polyester residues as fillers for polymer materials such as plastics and rubber will lead to thermo-oxidative aging degradation of polymer materials; heavy calcium waste residues containing PAM are used in flue gas wet desulfurization systems. It leads to the solidification of limestone slurry and the blockage of equipment; the heavy calcium waste residue containing polymer residues is used to burn lime, which is easy to cause calcium carbonate to burst and agglomerate during high temperature calcination, and block the kiln. Therefore, in view of the characteristics of difficult sedimentation of small particles and high unsaturated polyester content in the artificial granite heavy calcium waste residue, a differentiated use of granite cutting fluid is proposed.

SUMMARY OF THE INVENTION

The purpose of the present invention is to provide a comprehensive utilization method of the granite cutting waste liquid, so as to solve the deficiencies in the prior art. Low cost and refined treatment are conducive to promoting the high-value utilization of stone solid waste.

The invention provides a comprehensive utilization method of granite cutting waste liquid, comprising the following steps:

(1) Add low surface energy substances to the stone cutting waste liquid;

(2) For waste liquids such as gypsum and lime, the precipitation process is used to separate the large particle waste residue with low unsaturated resin content;

For solutions with difficult precipitation and high unsaturated resin content, wet modification of fillers for waterborne architectural coatings is used.

The above-mentioned comprehensive utilization method of granite cutting waste liquid, wherein, preferably, the low surface energy substance described in step (1) is an organosilicon surfactant.

In the above-mentioned comprehensive utilization method of granite cutting waste liquid, preferably, the added amount of the organosilicon surfactant is 0.01%-5% of the mass of the granite cutting waste liquid.

In the above-mentioned comprehensive utilization method of granite cutting waste liquid, preferably, the precipitation process in step (2) is based on the separation of granite cutting waste liquid in a horizontal flow sedimentation tank.

A kind of comprehensive utilization method of granite cutting waste liquid as mentioned above, wherein, preferably, described advection sedimentation tank takes granite waste slag liquid generation amount and component as object, relies on FLUENT software, adopts PISO algorithm to simulate, obtains. The flow field trace, volume fraction of suspended solids, flow velocity and other data of the granite waste residue liquid in the advection tank, and the concentration field and flow field distribution in the sedimentation tank are simulated at the same time, and the design is based on this data.

A kind of comprehensive utilization method of granite cutting waste liquid as described above, wherein, preferably, the particle size of the large particle waste residue with low unsaturated resin content described in step (2) is >15 μm, and the described difficult precipitation and no Particle size <15μm with high saturated resin content.

A kind of comprehensive utilization method of granite cutting waste liquid as mentioned above, wherein, it is preferred that the solution with difficult precipitation and high unsaturated resin content described in step (2) is prepared by evaporation combined with membrane filtration mode and has a solid content of 30- 50% small particle waste residue slurry, and then chemically modify the surface of the waste residue particles.

The above-mentioned comprehensive utilization method of granite cutting waste liquid, wherein, preferably, the method for chemically modifying the surface of the waste residue particles is: adding a hydrolyzed silane coupling agent during the stirring process.

The above-mentioned comprehensive utilization method of granite cutting waste liquid, wherein, preferably, the hydrolyzed silane solution is prepared from a silane coupling agent, a pH regulator and a solvent.

The above-mentioned comprehensive utilization method of granite cutting waste liquid, wherein, preferably, the silane coupling agent is γ-(2,3-glycidoxy)propyltrimethoxysilane, and the pH The regulator is ammonia water, the pH is adjusted to 9, and the solvent is a water-containing ethanol solution; the proportion by weight is: 0.1-20% of silane coupling agent, 1-20% of water, and ethanol as the balance.

Compared with the prior art, the present invention has the beneficial effects as follows: on the basis of analyzing the composition of the granite cutting fluid, a sedimentation tank is used to separate large particles of calcium carbonate in the granite waste liquid, and then an evaporation combined with a membrane filtration method is used to separate the unsaturated Resin and small particle calcium carbonate, no flocculant is added in the separation process, to achieve green separation; and according to the characteristics of the separated waste residue, differentiated application, improve the application effect of waste residue, and realize high-value utilization of slag. In addition, in order to improve the separation effect of the waste residue in the sedimentation tank, the design of the sedimentation tank structure combined with the addition of silicone surfactants is used to optimize the flow field of the waste liquid and reduce the surface tension of the solution, which not only achieves rapid separation, but also avoids unsaturated resin precipitation. , to separate high-purity large-particle calcium carbonate waste residue.

Description of drawings

Fig. 1 is the plan layout schematic diagram of the granite waste residue treatment tank of the embodiment of the present invention 1;

FIG. 2 is a schematic diagram of the plane layout of the granite waste residue treatment tank according to the second embodiment of the present invention.

Detailed ways

The embodiments described below with reference to the accompanying drawings are exemplary and are only used to explain the present invention, but not to be construed as a limitation of the present invention.

A method for comprehensive utilization of granite cutting waste liquid, comprising the following steps:

(1) Add low surface energy substances to the stone cutting waste liquid;

(2) For waste liquids such as gypsum and lime, the precipitation process is used to separate the large particle waste residue with low unsaturated resin content;

For solutions with difficult precipitation and high unsaturated resin content, wet modification of fillers for waterborne architectural coatings is used.

The low surface energy substance described in step (1) is an organosilicon surfactant.

The added amount of the organosilicon surfactant is 0.01%-5% of the mass of the stone cutting waste liquid.

The precipitation process described in step (2) is based on the separation of the granite cutting waste liquid based on the advection sedimentation tank.

The advection sedimentation tank takes the production volume and composition of the granite waste residue liquid as the object, relies on the FLUENT software, adopts the PISO algorithm to simulate, and obtains the flow field trace of the granite waste residue liquid in the advection tank, the volume fraction of suspended solids, the flow rate and other data. , Simultaneously simulate the concentration field and flow field distribution in the sedimentation tank, and design it based on the data.

In step (2), the particle size of the large-particle waste residue with low unsaturated resin content is greater than 15 μm, and the particle size of the difficult-to-precipitate and high unsaturated resin content particle size is less than 15 μm.

In step (2), the solution that is difficult to precipitate and has high unsaturated resin content is prepared by evaporation combined with membrane filtration to prepare a small particle waste residue slurry with a solid content of 30-50%, and then the surface of the waste residue particles is chemically modified. .

The method for chemically modifying the surface of the waste residue particles is as follows: adding a hydrolyzed silane coupling agent during the stirring process.

The hydrolyzed silane solution is prepared from a silane coupling agent, a pH regulator and a solvent.

The silane coupling agent is γ-(2,3-glycidoxy)propyltrimethoxysilane, the pH regulator is ammonia water, the pH is adjusted to 9, and the solvent is an aqueous ethanol solution; The proportion by weight is: 0.1-20% of silane coupling agent, 1-20% of water, and ethanol as the balance.

Embodiment 1 of the present invention:

The flow rate of the granite waste residue in a granite company is 1 ton/hour, and the mass fraction of solid particles in the waste liquid is 48%. Relying on the FLUENT software (Mixture model and standard κ-ε flocculation model), the PISO algorithm is used to simulate the granite. The flow field trace, volume fraction of suspended solids, flow rate and other data of the waste residue liquid in the advection tank were used to simulate the concentration field and flow field distribution in the sedimentation tank. The shape of the designed sedimentation tank is shown in Figure 1. As shown in the figure, the flow width of zone I of the sedimentation tank changes from narrow to wide, and then gradually widens (that is, a narrow-wide-narrow structure). Silicon surfactant, the addition rate is 10 kg/hour, and then the width of the channel narrows, which leads to a faster flow rate of the waste liquid, which is conducive to the uniform mixing of the waste liquid and the surfactant.

The waste residue liquid enters Zone II, that is, the sedimentation tank. Because the width of the flow channel becomes larger, the flow rate of the waste residue liquid becomes slower, and the large particles hit the right measuring area of Zone II and settle, where large particles of calcium carbonate waste residue can be collected; It contains a large amount of unsaturated resin and small particles of calcium carbonate and flows to zone III. With the reduction of the channel width, the flow rate of the waste residue liquid increases to avoid the precipitation of solid particles.

The waste residue liquid enters the IV zone, that is, the concentration tank. The concentration tank is open, which is conducive to water evaporation, and a water purification membrane is connected to one side of the concentration tank, which is used to purify waste water to achieve solid-liquid separation. The high-concentration solution in the concentration tank is collected, and the silane solution is added during the stirring process to prepare a small particle waste residue slurry with a solid content of 40%.

The large-particle calcium carbonate waste collected in the sedimentation tank is filtered and dried to collect the sediment, which is used as building gypsum, which conforms to the GB T 9776-2008 building gypsum standard. The small-particle waste residue mud collected in the concentration tank is used as a filler for building exterior wall coatings, which conforms to the GB/T 9755-2001 water-based exterior wall national standard.

Embodiment 2 of the present invention:

The flow rate of the granite waste residue in a granite company is 2 tons/hour, and the mass fraction of solid particles in the waste liquid is 48%. Relying on the FLUENT software (Mixture model and standard κ-ε flocculation model), the PISO algorithm is used to simulate the granite. The flow field trace, volume fraction of suspended solids, flow rate and other data of the waste residue liquid in the advection tank, and the concentration field and flow field distribution in the sedimentation tank are simulated at the same time, and the shape of the sedimentation tank is designed (as shown in Figure 2). At the same time, silicone surfactant was added at the inlet of the waste residue liquid at a rate of 20 kg/hour.

The waste residue liquid passes through a sedimentation tank to complete the precipitation of large particles; and then passes through a concentration tank to prepare a small particle waste residue slurry with a solid content of 30%.

The large-particle calcium carbonate waste collected in the sedimentation tank is filtered and dried to collect the sediment, which is used as construction cement, which meets the GB175-2007 construction cement standard. The small particle waste residue mud collected in the concentration tank is used as a filler for road indicating paint, and the prepared paint is stable and scratch resistant.

Embodiment 3 of the present invention:

The flow rate of the granite waste residue liquid in a granite company is 5 tons/hour, and the mass fraction of solid particles in the waste liquid is 48%. Relying on the FLUENT software (Mixture model and standard κ-ε flocculation model), the PISO algorithm is used to simulate the granite stone. The flow field trace, suspended solids volume fraction, flow rate and other data of the waste residue liquid in the advection tank, and the concentration field and flow field distribution in the sedimentation tank are simulated at the same time, and the shape of the sedimentation tank is designed. At the same time, silicone surfactant was added at the inlet of the waste residue liquid at a rate of 5 kg/hour.

The waste residue liquid passes through the sedimentation tank to complete the precipitation of large particles; and then passes through the concentration tank to prepare small particle waste residue mud with a solid content of 40%.

The large particle calcium carbonate waste collected in the sedimentation tank is dried by pressure filtration to collect the sediment, which is used as a plastic filler, and the filler has good dispersibility. The small particle waste residue mud collected in the concentration tank is used as a filler for building exterior wall coatings, which conforms to the GB/T9755-2001 water-based exterior wall national standard.

Embodiment 4 of the present invention:

The flow rate of the granite waste residue in a granite company is 1 ton/hour, and the mass fraction of solid particles in the waste liquid is 48%. Relying on the FLUENT software (Mixture model and standard κ-ε flocculation model), the PISO algorithm is used to simulate the granite. The flow field trace, suspended solids volume fraction, flow rate and other data of the waste residue liquid in the advection tank, and the concentration field and flow field distribution in the sedimentation tank are simulated at the same time, and the shape of the sedimentation tank is designed. At the same time, silicone surfactant was added at the inlet of the waste residue liquid at a rate of 0.1 kg/hour.

The waste residue liquid passes through the sedimentation tank to complete the precipitation of large particles; and then passes through the concentration tank to prepare small particle waste residue mud with a solid content of 35%.

The large-particle calcium carbonate waste collected in the sedimentation tank is filtered and dried to collect the sediment, which is used as a granite filler, which conforms to the JC 908-2013 granite standard. The small-particle waste residue mud collected in the concentration tank is used as a filler for building exterior wall coatings, which conforms to the GB/T 9755-2001 water-based exterior wall national standard.

The structure, features and effects of the present invention have been described in detail above according to the embodiments shown in the drawings. The above are only the preferred embodiments of the present invention, but the scope of the present invention is not limited by the drawings. Changes made to the concept of the present invention, or modifications to equivalent embodiments with equivalent changes, shall fall within the protection scope of the present invention as long as they do not exceed the spirit covered by the description and drawings.

Claims (7)

1. A comprehensive utilization method of granite cutting waste liquid is characterized in that: the method comprises the following steps:

(1) adding a low surface energy substance into the granite cutting waste liquid;

(2) for gypsum and lime waste liquid, large-particle waste residues with low unsaturated resin content are separated by adopting a precipitation process;

for the solution which is difficult to precipitate and has high content of unsaturated resin, the filler for the water-based architectural coating is modified by adopting a wet method;

the precipitation process in the step (2) is based on the separation of the granite cutting waste liquid in a horizontal flow type precipitation tank; preparing small-particle waste residue slurry with the solid content of 30-50% by using the solution which is difficult to precipitate and has high content of unsaturated resin in the step (2) in an evaporation and membrane filtration mode, and then carrying out surface chemical modification on waste residue particles;

the advection type sedimentation tank takes the generation amount and components of the granite waste residue liquid as objects, relies on FLUENT software, adopts PISO algorithm simulation to obtain the flow field trace, the volume fraction of suspended matters and the flow speed data of the granite waste residue liquid in the advection tank, simultaneously simulates the distribution condition of a concentration field and a flow field in the sedimentation tank, and is designed on the basis of the flow field trace, the volume fraction and the flow speed data;

the region I of the sedimentation tank flows to a position where the width is gradually widened from narrow to wide and then gradually widened from narrow to wide, the flow speed of the waste liquid is slowed down, the organic silicon surfactant is added at the position, the adding speed is 10 kg/h, and then the flow speed of the waste liquid is quickened due to the narrowing of the width of the flow channel, so that the waste liquid and the surfactant can be uniformly mixed;

the waste residue liquid enters a zone II, namely a sedimentation tank, because the width of a flow channel is increased, the flow velocity of the waste residue liquid is reduced, large particles impact a right measurement area of the zone II and are precipitated, and large-particle calcium carbonate waste residues can be collected at the position; at the moment, the waste liquid contains a large amount of unsaturated resin and small calcium carbonate particles, flows to a region III, and the flow velocity of the waste residue liquid is increased along with the reduction of the width of a flow channel, so that the precipitation of solid particles is avoided;

and enabling the waste residue liquid to enter an IV area, namely a concentration tank, wherein the concentration tank is open and is beneficial to water evaporation, one side of the concentration tank is connected with a water purification film for purifying waste water to realize solid-liquid separation, high-concentration solution in the concentration tank is collected, and silane solution is added in the stirring process, so that the small-particle waste residue slurry with the solid content of 40% is prepared.

2. The comprehensive utilization method of the waste cutting fluid of the granite as claimed in claim 1, which is characterized in that: in the step (1), the low surface energy substance is an organic silicon surfactant.

3. The comprehensive utilization method of the waste cutting fluid of the granite according to claim 2, characterized in that: the addition amount of the organic silicon surfactant is 0.01-5% of the mass of the granite cutting waste liquid.

4. The comprehensive utilization method of the waste cutting fluid of the granite as claimed in claim 1, which is characterized in that: in the step (2), the particle size of the large-particle waste residue with low content of unsaturated resin is more than 15 μm, and the particle size of the particles which are difficult to precipitate and have high content of unsaturated resin is less than 15 μm.

5. The comprehensive utilization method of the waste cutting fluid of the granite as claimed in claim 1, which is characterized in that: the method for carrying out surface chemical modification on the waste residue particles comprises the following steps: adding a hydrolytic silane coupling agent in the stirring process.

6. The comprehensive utilization method of the waste cutting fluid of the granite according to claim 5, characterized in that: the hydrolyzed silane solution is prepared from a silane coupling agent, a pH regulator and a solvent.

7. The comprehensive utilization method of the waste cutting fluid of the granite as claimed in claim 6, characterized in that: the silane coupling agent is gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane, the pH regulator is ammonia water, the pH is regulated to 9, and the solvent is an aqueous ethanol solution;

the weight ratio is as follows: 0.1-20% of silane coupling agent, 1-20% of water and the balance of ethanol.

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