CN112552922A - Easily-degradable environment-friendly dispersing foaming agent for mudstone geological shield and preparation method thereof - Google Patents
Easily-degradable environment-friendly dispersing foaming agent for mudstone geological shield and preparation method thereof Download PDFInfo
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Abstract
The invention relates to an easily degradable environment-friendly dispersing foaming agent for a mudstone geological shield and a preparation method thereof, wherein the foaming agent comprises the following raw materials in percentage by weight: 5-15% of alkyl ethyl sulfonate, 2-5% of rhamnolipid, 1-3% of lactate, 0.5-1% of carrageenan, 1-3% of citric acid, 0.5-2% of potassium tannate, 0.2-0.7% of chitosan and the balance of water. The raw materials adopted by the invention can be rapidly degraded by natural environment microorganisms, and have no secondary toxic and side products, thus showing the characteristics of huge environmental protection. The prepared foaming agent has the advantages of small environmental influence, strong foaming capacity, good foam stability, high mudstone dispersing speed, excellent muck improving effect and the like. The technical problems that the traditional foaming agent has large pollution to soil and water environment, poor mudstone dispersing effect and the like are solved, the backfill processing way of the shield muck is enlarged, the efficiency of the mudstone geological shield is increased, the shield construction cost is reduced, and the environmental protection and economic benefits are obvious.
Description
Technical Field
The invention relates to the technical field of shield construction, in particular to an easily degradable environment-friendly dispersing foaming agent for a mudstone geological shield and a preparation method thereof.
Background
At present, urban rail transit engineering construction is greatly promoted in various domestic large and medium-sized cities, and the most common construction mode is an earth pressure balance shield, because the earth pressure balance shield has the technical and economic advantages of wide applicable geology, high construction efficiency, low equipment cost investment (relative to a slurry balance shield), low construction cost and the like. Generally, various geologies are involved in a short shield distance, shield technicians need to improve muck at the front end of a cutter head and in a soil bin in order to improve shield efficiency, reduce cutter head abrasion and improve shield construction safety, and years of engineering application experience shows that the foaming agent is widely used due to the characteristics of convenience in application, excellent improvement effect, good economy and the like. Particularly aiming at clay geology and mudstone geology, the foaming agent shows good dispersion characteristic, can greatly improve the residue soil discharge efficiency, and shows huge application advantages. However, with the improvement of civilization and environmental protection construction requirements, the residual foaming agent in the muck is required to have good natural degradation capability under environmental conditions, and the traditional foaming agent mostly adopts ethoxynonyl phenols and lauryl polyoxyethylene surfactants as main components, so that the environmental microbial degradation performance is poor, and the environmental protection requirements cannot be met.
Patent CN110935393A discloses an environmental-friendly foaming agent and a preparation method thereof, wherein the main components of the foaming agent disclosed in the patent are sodium dodecyl sulfate, polyoxyethylene octylphenol ether, polyoxyethylene alkylphenol ether, preservative and the like, and the polyoxyethylene octylphenol ether and the polyoxyethylene alkylphenol ether have poor environmental degradation performance. Patent CN109628076A discloses a foaming agent composition for earth pressure balance shield and its preparation method, which uses lipopeptide surfactant, sophorolipid, welan gum and soybean protein as main components of foaming agent, and uses biodegradable raw materials with better environmental protection performance, but does not mention the dispersion performance of foaming agent.
At present, the invention and the manufacture of the environment-friendly shield foaming agent which is easily and rapidly degraded by environmental microorganisms are the key development direction of the shield foaming agent technology, and the technical problem to be solved is to realize rapid environmental biodegradation of all components of the foaming agent while ensuring the basic improvement effect and the strong dispersion performance of the foaming agent.
Disclosure of Invention
The invention aims to solve the technical problem of providing an environment-friendly foaming agent for a mudstone geological shield, which has high environmental microbial degradation speed and good clay dispersion function, and a preparation method thereof.
In order to solve the technical problems, the invention adopts the following technical scheme: an easily degradable environment-friendly dispersing foaming agent for a mudstone geological shield is composed of the following raw materials in percentage by weight: 5-15% of alkyl ethyl sulfonate, 2-5% of rhamnolipid, 1-3% of lactate, 0.5-1% of carrageenan, 1-3% of citric acid, 0.5-2% of potassium tannate, 0.2-0.7% of chitosan and the balance of water.
Further, the number of straight-chain alkyl carbon of the alkyl ethyl sulfonate is 10-14.
Further, the rhamnolipid is obtained by fermenting pseudomonas aeruginosa, the critical micelle concentration CMC of the rhamnolipid is not more than 22.5mg/L, and the surface tension of water can be reduced to be less than 31.5 mN/m.
Further, the lactate is sodium lactate or potassium lactate or a mixture of sodium lactate and potassium lactate.
Further, the carrageenan is a mixture of K-type carrageenan, I-type carrageenan and lambda-type carrageenan, wherein the total mass of the K-type carrageenan and the I-type carrageenan is more than or equal to 90%.
Further, the deacetylation degree of the chitosan is 70-85%.
The invention also provides a preparation method of the easily degradable environment-friendly dispersing foaming agent for the mudstone geological shield, which comprises the following steps:
(1) according to the mass percent of each component, putting carrageenan and water into a stirring kettle at normal temperature, stirring and feeding, then slowly heating up under the stirring state, wherein the stirring speed is 200-300 r/min, the heating speed is 5 ℃/10min, keeping the temperature and stirring for 1-2 h after the temperature is raised to 75-85 ℃, and then stopping heating;
(2) according to the mass percentage of each component, after the solution obtained in the step (1) is cooled to 50 ℃, alkyl ethyl sulfonate, rhamnolipid, potassium tannate and chitosan are added into the solution at one time, and then the solution is continuously stirred for 0.5 to 1 hour at the stirring speed of 1000 to 1500 r/min;
(3) and (3) after the solution obtained in the step (2) is cooled to below 35 ℃, adding lactate and citric acid into the solution according to the mass percentage, and continuously stirring for 15-30 min at the stirring speed of 1000-1500 r/min to obtain the easily-degradable environment-friendly dispersing foaming agent for the mudstone geological shield.
The main technical principle of the invention is as follows:
(1) the alkyl ethyl sulfonate and the rhamnolipid which play a foaming role are both anionic surfactants, have good compatibility, can play a foaming role in a synergistic manner, ensure that the foaming agent has a larger foaming multiple, and can be quickly degraded by microorganisms in soil.
(2) The sulfonate group in the alkyl ethyl sulfonate and the lipid group in the rhamnolipid form hydrogen bonds with water after hydrolysis, so that the common property of improving the viscosity and elasticity of a bubble film is achieved, but lactate ions are introduced into a bubble film solution, the connection between the surfactant molecules in the bubble film is enhanced through the serial connection effect of a large number of hydrogen bonds by utilizing the characteristic that the lactate is easy to form the hydrogen bonds with water because the surfactant molecules are regularly arranged on the surface of the bubble film and are far away, and the acting force between the surfactant molecules is weak, so that the elasticity of the bubble film still cannot meet the requirement of resisting the deformation of the external action, and a large number of surfactant molecules are connected in series to form a whole, so that the elasticity of the bubble film is improved.
(3) The characteristic that the viscosity of the solution can be increased after the carrageenan is swelled is utilized, the viscosity of the bubble film solution is improved, and the technical problems of poor foam stability and high breaking speed after foaming are well solved, wherein the carrageenan is easy to degrade quickly by microorganisms.
(4) Citric acid and potassium tannate are used as clay particle dispersing components, the two substances are moderate in molecular weight and can be adsorbed on clay particles to exert the viscosity reduction dispersing effect, the potassium tannate is high in adsorption speed and exerts the early-stage dispersing function, the citric acid is relatively low in adsorption speed and mainly exerts the later-stage dispersing function, and the mud rock muck can be continuously improved at the positions of a cutter head and a soil bin even if foam is added at the position of the cutter head at one time by virtue of the synergistic use of the two substances.
(5) Chitosan which is easily degraded by environmental microorganisms is used as an antistaling agent component of the foaming agent to replace the traditional toxic bacteriostatic component, so that the environmental protection characteristic of the whole foaming agent is ensured while the quality of a system is guaranteed.
The invention has the beneficial effects that:
(1) all raw material components adopted by the invention are non-toxic substances, a large number of components are prepared by biological fermentation, all the components can be rapidly degraded by natural microorganisms in soil, the 2d degradation rate of organic matters in the whole foaming agent system reaches more than 90 percent, the preparation scheme of the environment-friendly shield foaming agent is provided in a real sense, the environment-friendly and social benefits are obvious, and meanwhile, the foaming agent is endowed with a good clay dispersion function, so that the effect of improving the muck fluidity and plasticity of the shale geological shield is achieved.
(2) The low critical micelle concentration surfactant is used as the main bubble component of the foaming agent, so that the low foaming agent can have higher foaming multiplying power at lower concentration, when the mass concentration of the prepared foaming agent is 2 per mill, the invoice multiplying power is more than 20 times, the half-life period of bubbles reaches 35min, the using amount of the foaming agent is reduced, and the environmental protection characteristic of improving the muck is further improved. Meanwhile, the use cost of the degradable environment-friendly foaming agent is reduced, the problem of high application cost existing in the foaming agent is solved, the use of the foaming agent in more shield projects is greatly promoted, and the economic benefit is remarkable.
(3) According to the invention, the two dispersants have different adsorption speeds on the clay particle surface, so that the foaming agent shows the effect of continuously dispersing the mudstone, compared with the defect that the conventional mudstone texture shield construction needs to add the foaming agent at the positions of a cutter head, a soil bin and a screw conveyor for multiple times to achieve the effect of continuously improving the muck, the mudstone muck can be continuously improved once only by adding the foaming agent at the front end of the cutter head, the muck improvement process is simplified, and the consumption of the foaming agent is reduced.
Detailed Description
The present invention will be further illustrated below with reference to specific embodiments, which are to be understood as merely illustrative and not limitative of the scope of the present invention. The various starting materials used in the following examples and comparative examples, unless otherwise specified, are all commercially available products well known in the art:
example 1
The easily-degradable environment-friendly dispersing foaming agent for the mudstone geological shield comprises the following raw materials in percentage by weight: 10% of alkyl ethyl sulfonate, 3% of rhamnolipid, 2% of sodium lactate, 0.8% of carrageenan, 2% of citric acid, 1.2% of potassium tannate, 0.5% of chitosan and the balance of water; wherein the linear alkyl carbon number of the alkyl ethyl sulfonate is 14; the rhamnolipid is obtained by fermenting pseudomonas aeruginosa, the critical micelle concentration CMC of the rhamnolipid is 22.5mg/L, and the surface tension of water can be reduced to 31.5 mN/m; the carrageenan is a mixture of K-type carrageenan, I-type carrageenan and lambda-type carrageenan, wherein the total mass of the K-type carrageenan and the I-type carrageenan accounts for 90 percent; the degree of deacetylation of chitosan was 80%.
The preparation method of the easily degradable environment-friendly dispersing foaming agent for the mudstone geological shield comprises the following steps:
(1) according to the mass percent of each component, putting carrageenan and water into a stirring kettle at normal temperature, stirring and feeding, then slowly heating up under the stirring state, wherein the stirring speed is 250r/min, the heating speed is 5 ℃/10min, keeping the temperature and stirring for 1.5h after the temperature is raised to 80 ℃, and then stopping heating;
(2) according to the mass percent of each component, after the solution obtained in the step (1) is cooled to 50 ℃, alkyl ethyl sulfonate, rhamnolipid, potassium tannate and chitosan are added into the solution at one time, and then the solution is continuously stirred for 0.7h at the stirring speed of 1300 r/min;
(3) and (3) after the solution obtained in the step (2) is cooled to 35 ℃, adding lactate and citric acid into the solution according to the mass percentage, and continuously stirring for 22min at the stirring speed of 1200r/min to obtain the easily-degradable environment-friendly dispersing foaming agent for the mudstone geological shield.
The easily degradable environment-friendly dispersing foaming agent for the mudstone geological shield prepared by the embodiment has the following properties: 2d, the degradation rate of organic matters is 93 percent, the foaming ratio is 23 times, the half life period is 45min, and the permeability coefficient of the improved residue soil is 0.6 multiplied by 10-6cm/s, improving the initial 18cm of sludges slump and standing for 15min and then 17 cm.
Example 2
The easily-degradable environment-friendly dispersing foaming agent for the mudstone geological shield comprises the following raw materials in percentage by weight: 5% of alkyl ethyl sulfonate, 2% of rhamnolipid, 1% of potassium lactate, 0.5% of carrageenan, 1% of citric acid, 0.5% of potassium tannate, 0.2% of chitosan and the balance of water; wherein the linear alkyl carbon number of the alkyl ethyl sulfonate is 10; the rhamnolipid is obtained by fermenting pseudomonas aeruginosa, the critical micelle concentration CMC of the rhamnolipid is 22.1mg/L, and the surface tension of water can be reduced to 31.1 mN/m; the carrageenan is a mixture of K-type carrageenan, I-type carrageenan and lambda-type carrageenan, wherein the total mass of the K-type carrageenan and the I-type carrageenan accounts for 92 percent; the degree of deacetylation of chitosan was 70%.
The preparation method of the easily degradable environment-friendly dispersing foaming agent for the mudstone geological shield comprises the following steps:
(1) according to the mass percent of each component, putting carrageenan and water into a stirring kettle at normal temperature, stirring and feeding, then slowly heating up under the stirring state, wherein the stirring speed is 200r/min, the heating speed is 5 ℃/10min, keeping the temperature and stirring for 2h after the temperature is raised to 75 ℃, and then stopping heating;
(2) according to the mass percent of each component, after the solution obtained in the step (1) is cooled to 50 ℃, alkyl ethyl sulfonate, rhamnolipid, potassium tannate and chitosan are added into the solution at one time, and then the solution is continuously stirred for 1h at the stirring speed of 1000 r/min;
(3) and (3) after the solution obtained in the step (2) is cooled to 35 ℃, adding lactate and citric acid into the solution according to the mass percentage, and continuously stirring for 15min at the stirring speed of 1500r/min to obtain the easily-degradable environment-friendly dispersing foaming agent for the mudstone geological shield.
The easily degradable environment-friendly dispersing foaming agent for the mudstone geological shield prepared by the embodiment has the following properties: 2d organic matter degradation rate of 91%, foaming ratio of 21 times, half life period of 40min, improved residue soil permeability coefficient of 0.5 multiplied by 10-6cm/s, improving the initial slump of the residue soil by 17cm, and standing for 15min for 16 cm.
Example 3
The easily-degradable environment-friendly dispersing foaming agent for the mudstone geological shield comprises the following raw materials in percentage by weight: 15% of alkyl ethyl sulfonate, 5% of rhamnolipid, 3% of sodium lactate, 1% of carrageenan, 3% of citric acid, 2% of potassium tannate, 0.7% of chitosan and the balance of water; wherein the linear alkyl carbon number of the alkyl ethyl sulfonate is 12; the rhamnolipid is obtained by fermenting pseudomonas aeruginosa, the critical micelle concentration CMC of the rhamnolipid is 22.3mg/L, and the surface tension of water can be reduced to 31.2 mN/m; the carrageenan is a mixture of K-type carrageenan, I-type carrageenan and lambda-type carrageenan, wherein the total mass of the K-type carrageenan and the I-type carrageenan accounts for 95 percent; the degree of deacetylation of chitosan was 85%.
The preparation method of the easily degradable environment-friendly dispersing foaming agent for the mudstone geological shield comprises the following steps:
(1) according to the mass percent of each component, putting carrageenan and water into a stirring kettle at normal temperature, stirring and feeding, then slowly heating up under the stirring state, wherein the stirring speed is 300r/min, the heating speed is 5 ℃/10min, keeping the temperature and stirring for 1h after the temperature is raised to 85 ℃, and then stopping heating;
(2) according to the mass percent of each component, after the solution obtained in the step (1) is cooled to 50 ℃, alkyl ethyl sulfonate, rhamnolipid, potassium tannate and chitosan are added into the solution at one time, and then the solution is continuously stirred for 0.5h at the stirring speed of 1500 r/min;
(3) and (3) after the solution obtained in the step (2) is cooled to 35 ℃, adding lactate and citric acid into the solution according to the mass percentage, and continuously stirring for 30min at the stirring speed of 1000r/min to obtain the easily-degradable environment-friendly dispersing foaming agent for the mudstone geological shield.
The easily degradable environment-friendly dispersing foaming agent for the mudstone geological shield prepared by the embodiment has the following properties: 2d organic matter degradation rate of 92 percent, foaming ratio of 22 times, half life period of 45min and improved residue soil permeability coefficient of 0.6 multiplied by 10-6cm/s, improving the initial 18cm of sludges slump and standing for 15min for 16 cm.
Comparative experiment 1
To facilitate an understanding of the effect of the materials of the present invention on the properties of the materials, another 6 examples of the present invention are provided below for comparison with 5 comparative examples, each example and each comparative formula is shown in table 1, the preparation method is the same as example 1 (comparative example, if no material is added, the procedure is still operating), among the materials:
the alkyl ethyl sulfonate has a linear alkyl carbon number of 14; the rhamnolipid is obtained by fermenting pseudomonas aeruginosa, the critical micelle concentration CMC of the rhamnolipid is 22.1mg/L, and the surface tension of water can be reduced to 31.1 mN/m; the lactate is potassium lactate; the carrageenan is a mixture of K-type carrageenan, I-type carrageenan and lambda-type carrageenan, wherein the total mass ratio of the K-type carrageenan to the I-type carrageenan is 92%, and the mass ratio of the K-type carrageenan to the I-type carrageenan is 1: 1; the deacetylation degree of chitosan is 82%;
TABLE 1 compositions (unit: weight percentage) of examples and comparative examples
The performance test results of the easily degradable environment-friendly dispersion foaming agent for mudstone geological shield in examples 4-9 and comparative examples 1-5 are shown in table 2:
TABLE 2 results of performance test of examples and comparative examples
Table 2 remarks illustrate: 1. all the performance data are measured by diluting the foaming agent to 2 per mill mass concentration; 2. when the residue soil is improved, 20L of foaming agent with the mass concentration of 2 per thousand is added into each solid residue soil; 3. the effect of improving the slag soil is mainly evaluated by the permeability coefficient and the slump, and the permeability coefficient of less than 1.0 multiplied by 10 is generally required-6cm/s, preferably a slump of 15 to 20 cm.
It can be seen from the above that, the easily degradable environment-friendly dispersing foaming agent for the mudstone geological shield obtained by the technical scheme in the embodiments 1-9 meets the basic use requirements of the mudstone geological shield construction, and presents excellent environmental microbial degradation characteristics, while the foaming agent obtained in the comparative examples 1-5 is obviously inferior to the invention in performance, which shows that each raw material of alkyl ethyl sulfonate, rhamnolipid, lactate, carrageenan, citric acid, potassium tannate and chitosan has great influence on the performance of the foaming agent.
Comparative experiment 2
To facilitate an understanding of the effect of the linear alkyl carbon number of the alkyl ethyl sulfonate on the performance of the foam of the present invention, on the basis of example 1, alkyl ethyl sulfonate having a linear alkyl carbon number of 7 was used instead as comparative example 6, and alkyl ethyl sulfonate having a linear alkyl carbon number of 17 was used instead as comparative example 7;
in order to facilitate understanding of the effect of CMC, the critical micelle concentration of rhamnolipids, on the performance of the foaming agent of the invention, on the basis of example 1, rhamnolipids with a critical micelle concentration of CMC of 23.0mg/L, obtained by fermentation of pseudomonas aeruginosa, were used instead as comparative example 8;
in order to facilitate understanding of the influence of the specific composition of carrageenan on the performance of the foaming agent, based on example 1, carrageenan with the mass ratio of K-type carrageenan to I-type carrageenan of 1:1 and the total mass ratio of K-type carrageenan to I-type carrageenan of 85% is used instead, as comparative example 9, carrageenan without lambda-type carrageenan is used instead, the carrageenan consists of K-type carrageenan and I-type carrageenan, and the carrageenan with the mass ratio of K-type carrageenan to I-type carrageenan of 1:1 is used as comparative example 10;
the results of the performance tests of the foams obtained in the above respective proportions are shown in table 3:
table 3 comparative experiment 2 test results
It should be understood that the examples and embodiments described herein are for illustrative purposes only and are not intended to limit the scope of the present disclosure, and that various modifications or changes in light thereof will be suggested to persons skilled in the art and are to be included within the spirit and purview of this disclosure.
Claims (7)
1. The easily degradable environment-friendly dispersing foaming agent for the mudstone geological shield is characterized in that: the composite material consists of the following raw materials in percentage by weight: 5-15% of alkyl ethyl sulfonate, 2-5% of rhamnolipid, 1-3% of lactate, 0.5-1% of carrageenan, 1-3% of citric acid, 0.5-2% of potassium tannate, 0.2-0.7% of chitosan and the balance of water.
2. The easily degradable environment-friendly dispersing foaming agent for the mudstone geological shield as claimed in claim 1, which is characterized in that: the number of straight chain alkyl carbon of the alkyl ethyl sulfonate is 10-14.
3. The easily degradable environment-friendly dispersing foaming agent for the mudstone geological shield as claimed in claim 1, which is characterized in that: the rhamnolipid is obtained by fermenting pseudomonas aeruginosa, the critical micelle concentration CMC of the rhamnolipid is not more than 22.5mg/L, and the surface tension of water can be reduced to be less than 31.5 mN/m.
4. The easily degradable environment-friendly dispersing foaming agent for the mudstone geological shield as claimed in claim 1, which is characterized in that: the lactate is sodium lactate or potassium lactate or a mixture of sodium lactate and potassium lactate.
5. The easily degradable environment-friendly dispersing foaming agent for the mudstone geological shield as claimed in claim 1, which is characterized in that: the carrageenan is a mixture of K-type carrageenan, I-type carrageenan and lambda-type carrageenan, wherein the total mass ratio of the K-type carrageenan to the I-type carrageenan is more than or equal to 90%.
6. The easily degradable environment-friendly dispersing foaming agent for the mudstone geological shield as claimed in claim 1, which is characterized in that: the deacetylation degree of the chitosan is 70-85%.
7. The preparation method of the easily degradable environment-friendly dispersing foaming agent for the mudstone geological shield as claimed in any one of claims 1 to 6, which is characterized by comprising the following steps: the method comprises the following steps:
(1) according to the mass percent of each component, putting carrageenan and water into a stirring kettle at normal temperature, stirring and feeding, then slowly heating up under the stirring state, wherein the stirring speed is 200-300 r/min, the heating speed is 5 ℃/10min, keeping the temperature and stirring for 1-2 h after the temperature is raised to 75-85 ℃, and then stopping heating;
(2) according to the mass percentage of each component, after the solution obtained in the step (1) is cooled to 50 ℃, alkyl ethyl sulfonate, rhamnolipid, potassium tannate and chitosan are added into the solution at one time, and then the solution is continuously stirred for 0.5 to 1 hour at the stirring speed of 1000 to 1500 r/min;
(3) and (3) after the solution obtained in the step (2) is cooled to below 35 ℃, adding lactate and citric acid into the solution according to the mass percentage, and continuously stirring for 15-30 min at the stirring speed of 1000-1500 r/min to obtain the easily-degradable environment-friendly dispersing foaming agent for the mudstone geological shield.
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| CN113651550A (en) * | 2021-08-16 | 2021-11-16 | 中铁十局集团有限公司 | Mudstone and clay geological shield muck improvement dispersant, and preparation and application thereof |
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