High-efficiency composite environment-friendly deodorizing passivation cleaning agent and preparation method thereof

Abstract

The application discloses a high-efficiency composite environment-friendly deodorization passivation cleaning agent and a preparation method thereof, relates to the technical field of cleaning agents, and discloses the cleaning agent which is prepared by compounding a slow-release oxidant, a composite deodorant, a compounded corrosion inhibitor, chitosan quaternary ammonium salt, plant polysaccharide and the like as core functional components, and other additives and deionized water. The high-efficiency composite environment-friendly deodorization passivation cleaning agent has the advantages of high cleaning and deodorization efficiency, low metal corrosion, good system stability, environmental protection and practicality, and is suitable for industrial equipment vulcanization dirt cleaning and malodorous treatment scenes.

Description

Technical Field

[0001] This invention relates to the field of cleaning agent technology, and in particular to a high-efficiency, composite, environmentally friendly deodorizing and passivating cleaning agent and its preparation method. Background Technology

[0002] In petrochemical, oil refining, and natural gas processing, ferrous sulfide (FeS) deposits often form on the inner walls of equipment and pipelines due to the reaction of sulfur compounds in the feedstock with iron. These deposits are prone to spontaneous combustion upon contact with air during maintenance, producing large amounts of malodorous and toxic gases such as sulfur dioxide and hydrogen sulfide. This not only causes equipment corrosion but also seriously threatens the health of operators and production safety. Traditional treatment methods often involve mechanical cleaning or strong acid cleaning agents. However, mechanical cleaning is prone to generating sparks that can cause fires, while strong acid cleaning presents problems such as equipment corrosion, difficulty in waste liquid treatment, and severe environmental pollution.

[0003] Currently, there are some deodorizing and passivating agents for FeS on the market. These include solid passivating agents composed of oxidants, activators, passivating agents, and hydrogen sulfide inhibitors, designed to convert FeS into stable water-soluble complexes and reduce H2S generation; or environmentally friendly pickling and passivating pastes composed of environmentally friendly pickling agents, composite passivating agents, and thixotropic thickening systems, replacing highly corrosive inorganic acids to meet environmental requirements. However, existing deodorizing and passivating cleaning agents still have significant drawbacks in practical applications: on the one hand, the oxidants in traditional formulations are prone to failure and instability, leading to an uncontrollable cleaning process; on the other hand, single-component deodorizers cannot simultaneously achieve the complexation stability of heavy metal ions and the complete decomposition of malodorous gases, easily causing secondary pollution, and have limited penetration and deposit removal capabilities on complex equipment surfaces.

[0004] On the other hand, the commonly used industrial cleaning processes still have problems such as large wastewater generation, high steam consumption, long cleaning time, and high labor intensity. Moreover, with increasingly stringent environmental standards, existing cleaning agents are no longer able to meet the requirements of "high-efficiency passivation, thorough deodorization, non-corrosiveness, easy degradation, and compliant wastewater discharge".

[0005] To address the aforementioned issues, invention patent document CN102912366A discloses a ferrous sulfide passivating cleaning agent, comprising: sodium bicarbonate, sodium hypochlorite, tetrasodium ethylenediaminetetraacetate (EDTA-tetrasodium), potassium ferrate, a surfactant, and water. This passivating cleaning agent offers advantages such as safety, high efficiency, environmental friendliness, low cost, and the ability to absorb toxic and harmful gases. The potassium ferrate component not only has bactericidal properties but is also environmentally friendly, making it a novel, highly efficient, and multifunctional passivating agent integrating oxidation, adsorption, flocculation, coagulation aid, sterilization, insecticidal effect, and deodorization. This potassium ferrate component boasts numerous advantages, including good bactericidal effect, low dosage, rapid action, multiple functions, good safety, ease of use, and wide application. However, this patent uses a combination of potassium ferrate and sodium hypochlorite, resulting in excessive oxidizing power and severe corrosion of copper and some alloy equipment. Furthermore, the potassium ferrate-containing aqueous solution exhibits poor stability and is prone to decomposition and failure, failing to meet the industrial application requirements of low corrosion, long-term stability, and easy emission.

[0006] Therefore, developing an environmentally friendly passivation cleaning agent with high passivation and deodorization efficiency, extremely low corrosivity, non-clogging of equipment, and easy waste liquid treatment is of great significance for promoting safe and green production in the petrochemical industry. Summary of the Invention

[0007] To address the problems and defects in the aforementioned technologies, this invention provides a highly efficient, composite, environmentally friendly deodorizing and passivating cleaning agent and its preparation method. This passivating cleaning agent has high passivation and deodorization efficiency and good effect, extremely low corrosivity, does not clog equipment, and its waste liquid is easy to treat.

[0008] To achieve the above objectives, the technical solution adopted by this invention is as follows: a high-efficiency composite environmentally friendly deodorizing and passivating cleaning agent, which, by mass percentage, consists of the following components: 7-14 wt% slow-release oxidant, 3-6 wt% dispersant, 2-5 wt% penetrant, 0.8-2.5 wt% corrosion inhibitor, 3-5 wt% activator, 3-5 wt% auxiliary passivating agent, 8-10 wt% composite deodorizer, 1-3 wt% synergist, 0.5-1.2 wt% β-cyclodextrin containing plant-based deodorizing extract, 1.5-3 wt% chitosan quaternary ammonium salt, 0.8-1.2 wt% plant polysaccharide, and the balance being deionized water; the slow-release oxidant is a low-temperature co-soluble composite salt of sodium percarbonate and sodium gluconate; the corrosion inhibitor includes 3-mercaptopropyltriethoxysilane; the composite deodorizer is a compound of ultrafine sodium silicate, hydroxyethylidene diphosphonic acid, and microbial agent in a mass ratio of (3-5):(1-3):(0.1-0.3).

[0009] Preferably, the method for preparing the slow-release oxidant includes the following steps: adding deionized water to a reaction vessel, heating to 40-45°C, adding sodium percarbonate and sodium gluconate, stirring to dissolve, adjusting the pH to 6.5-7.0, keeping warm for 30-40 minutes, cooling to crystallize, drying and pulverizing to obtain the slow-release oxidant.

[0010] Preferably, the molar ratio of sodium percarbonate, sodium gluconate, and deionized water is 1:(0.8-1.2):(6-10).

[0011] Preferably, the dispersant is sodium lignosulfonate.

[0012] Preferably, the penetrant is a fatty alcohol polyoxyethylene ether.

[0013] Preferably, the corrosion inhibitor is a compound of sodium sarcosinate, 2-mercaptobenzimidazole, and 3-mercaptopropyltriethoxysilane in a mass ratio of 1:(1-2):(0.8-1.2).

[0014] Preferably, the activator is at least one of ammonium nitrate and ammonium sulfate.

[0015] Preferably, the auxiliary passivating agent is tetrahydroxymethylphosphoric acid.

[0016] Preferably, the ultrafine sodium silicate has a particle size of 200-325 mesh; the microbial agent is an effective live bacteria powder, formulated by compounding Bacillus licheniformis AS 1.813 and Bacillus subtilis CGMCC 1.3358 at a dry basis mass ratio of (1-3):1; wherein the effective live count of Bacillus licheniformis is ≥2.0 × 10⁻⁶. 9 CFU / g, effective viable count of Bacillus subtilis ≥2.0×10⁻⁶ 9 CFU / g.

[0017] Preferably, the synergist is at least one of disodium ethylenediaminetetraacetate and potassium pyrophosphate.

[0018] Preferably, the method for preparing the β-cyclodextrin containing the plant-based deodorizing extract includes the following steps: dissolving β-cyclodextrin in deionized water at 58-62°C to form a saturated solution; slowly adding the plant-based deodorizing extract dropwise to the above cyclodextrin aqueous solution at a core-to-wall ratio of (7-8):1, with the addition time controlled at 30-40 min; stirring and incorporating the extract under constant temperature and sealed conditions for 2.5-3.5 h; allowing it to cool naturally to room temperature; and aging it for 10-14 h to allow the inclusion complex to fully crystallize and precipitate; filtering; washing the filter cake with deionized water; vacuum drying at 40-50°C; and pulverizing it through an 80-100 mesh sieve to obtain the β-cyclodextrin-incorporated plant-based deodorizing extract inclusion complex powder.

[0019] Preferably, the preparation method of the plant-based deodorizing extract includes the following steps: mixing fresh and dried peppermint, artemisia, rosemary, and tea tree, pulverizing them, and passing them through a 20-40 mesh sieve to obtain a plant mixture powder; adding 6-10 times the mass of deionized water to the plant mixture powder, soaking for 30-60 minutes, and then heating to 95-100℃ and decocting for 2-4 hours; filtering the extract coarsely and centrifuging to remove solid residues, and collecting the supernatant; passing the supernatant through rotary evaporation and fine filtration through a microporous membrane to obtain the plant-based deodorizing extract.

[0020] Preferably, the mass ratio of the fresh and dried mint, mugwort, rosemary, and tea tree is (2-4):(1-3):(3-5):3.

[0021] Preferably, the degree of substitution of the chitosan quaternary ammonium salt is 90%, and the number average molecular weight is 100,000.

[0022] Preferably, the plant polysaccharide is trehalose.

[0023] Another objective of this invention is to provide a method for preparing the aforementioned high-efficiency composite environmentally friendly deodorizing and passivating cleaning agent, comprising the following steps: mixing each component evenly according to the weight proportions, and allowing it to stand for 2-4 hours to mature, thereby obtaining the high-efficiency composite environmentally friendly deodorizing and passivating cleaning agent.

[0024] Due to the application of the above technical solution, the present invention has the following beneficial effects: (1) The high-efficiency composite environmentally friendly deodorizing and passivating cleaning agent and its preparation method disclosed in this invention achieve efficient and stable passivation and deodorization through the synergistic effect of the slow-release oxidant and each component, solving the pain points of easy failure of oxidant and excessive oxidizing power in the prior art. The low-temperature co-soluble composite salt of sodium percarbonate and sodium gluconate is used as the slow-release oxidant. Compared with the potassium ferrate and sodium hypochlorite compound system in the prior art, it can slowly release oxidizing substances, avoiding excessive local oxidizing power and corrosion of copper and alloy equipment. At the same time, it can synergize with the composite deodorant and β-cyclodextrin containing plant-based deodorizing extracts, which can not only efficiently convert FeS into stable complexes and completely inhibit the generation of malodorous gases such as hydrogen sulfide and sulfur dioxide, but also decompose residual malodorous substances through the synergistic effect of plant-based extracts and microbial agents, achieving the dual effect of "passivation + deodorization". Moreover, the stability of the oxidant is significantly improved, effectively extending the shelf life of the cleaning agent and solving the problems of uncontrollable cleaning process and secondary pollution in the existing formula.

[0025] (2) The high-efficiency composite environmentally friendly deodorizing and passivating cleaning agent and its preparation method disclosed in this invention achieve a balance between extremely low corrosion and high-efficiency cleaning by synergistic action of corrosion inhibitor, penetrant, and dispersant, overcoming the limitations of existing technologies in corroding equipment and weak penetration and stripping capabilities. The corrosion inhibitor is a compound of sodium sarcosinate, 2-mercaptobenzimidazole, and 3-mercaptopropyltriethoxysilane. Among them, 3-mercaptopropyltriethoxysilane can form a dense protective film on the surface of the equipment. With the synergistic effect of the other two corrosion inhibitors, the corrosion of the equipment by the cleaning agent is significantly reduced. Compared with the existing potassium ferrate compound system, the corrosion rate of copper and alloy equipment is significantly reduced. At the same time, the penetrant fatty alcohol polyoxyethylene ether and the dispersant sodium lignosulfonate work together to quickly penetrate into the gaps of FeS deposits on the inner wall of the equipment pipes, promoting the stripping of deposits. With the help of the dispersant, the agglomeration of the stripped deposits prevents them from clogging the equipment. This solves the problems of sparks generated by traditional mechanical cleaning and corrosion of equipment by strong acid cleaning, and significantly improves the cleaning efficiency and shortens the cleaning time.

[0026] (3) The high-efficiency composite environmentally friendly deodorizing and passivating cleaning agent and its preparation method disclosed in this invention achieve a breakthrough in environmental protection and long-lasting deodorization by synergistically combining plant-based components with microbial agents, chitosan quaternary ammonium salt, etc., and meeting stringent environmental protection standards. The β-cyclodextrin encapsulates the plant-based deodorizing extract and works synergistically with chitosan quaternary ammonium salt and plant polysaccharides (trehalose), which not only enhances the deodorizing effect but also improves the biodegradability of the cleaning agent. The antibacterial properties of chitosan quaternary ammonium salt can inhibit the growth of microorganisms and avoid secondary pollution of waste liquid. The synergistic effect of ultrafine sodium silicate, hydroxyethylidene diphosphonic acid and microbial agents in the composite deodorizing agent can not only complex the heavy metal ions generated during the cleaning process, but also degrade the organic pollutants in the waste liquid through microbial agents, so that the waste liquid can meet the discharge standards without complicated treatment, solving the problems of difficult waste liquid treatment and serious environmental pollution of existing cleaning agents. At the same time, the addition of plant-based components further reduces the irritation of the cleaning agent and improves the safety of operation.

[0027] (4) The high-efficiency composite environmentally friendly deodorizing and passivating cleaning agent and its preparation method disclosed in this invention optimize the cleaning process through the synergistic effect of each component, reduce the cost of industrial application, and solve the pain points of large wastewater volume, high steam consumption, and high labor intensity in existing processes. This cleaning agent can achieve high-efficiency cleaning without the assistance of high-temperature steam, and the synergistic effect of each component can improve the cleaning efficiency, shorten the cleaning time, and reduce the amount of wastewater generated. At the same time, the stability of the slow-release oxidant reduces the amount of cleaning agent used, and the synergistic effect of the auxiliary passivating agent tetramethyl phosphate and the synergist further improves the passivation effect, extends the service life of equipment, significantly reduces the production and environmental protection costs of enterprises, and helps the petrochemical industry to produce safely and greenly. Detailed Implementation

[0028] The following description is intended to disclose the invention and enable those skilled in the art to implement it. The preferred embodiments described below are merely examples, and other obvious variations will occur to those skilled in the art.

[0029] Example 1

[0030] A highly efficient, composite, environmentally friendly deodorizing and passivating cleaning agent, by weight percentage, comprises the following components: 7wt% slow-release oxidant, 3wt% dispersant, 2wt% penetrant, 0.8wt% corrosion inhibitor, 3wt% activator, 3wt% auxiliary passivating agent, 8wt% composite deodorizer, 1wt% synergist, 0.5wt% β-cyclodextrin containing plant-based deodorizing extract, 1.5wt% chitosan quaternary ammonium salt, 0.8wt% plant polysaccharide, with the balance being deionized water; the slow-release oxidant is a low-temperature co-soluble composite salt of sodium percarbonate and sodium gluconate; the corrosion inhibitor includes 3-mercaptopropyltriethoxysilane; the composite deodorizer is a compound of ultrafine sodium silicate, hydroxyethylidene diphosphonic acid, and microbial agent in a weight ratio of 3:1:0.1.

[0031] The method for preparing the slow-release oxidant includes the following steps: adding deionized water to a reaction vessel, heating to 40°C, adding sodium percarbonate and sodium gluconate, stirring to dissolve, adjusting the pH to 6.5, keeping warm for 30 minutes, cooling to crystallize, drying and pulverizing to obtain the slow-release oxidant; the molar ratio of sodium percarbonate, sodium gluconate and deionized water is 1:0.8:6.

[0032] The dispersant is sodium lignosulfonate; the penetrant is fatty alcohol polyoxyethylene ether; the corrosion inhibitor is sodium sarcosinate, 2-mercaptobenzimidazole, and 3-mercaptopropyltriethoxysilane compounded in a mass ratio of 1:1:0.8; the activator is ammonium nitrate; the auxiliary passivating agent is tetramethylolphosphine sulfate; the particle size of the ultrafine sodium silicate is 200 mesh; the microbial agent is effective live bacteria powder, compounded from Bacillus licheniformis AS 1.813 and Bacillus subtilis CGMCC 1.3358 in a dry basis mass ratio of 1:1; wherein the effective live count of Bacillus licheniformis is ≥2.0×10⁻⁶. 9 CFU / g, effective viable count of Bacillus subtilis ≥2.0×10⁻⁶ 9 CFU / g; the synergist is disodium ethylenediaminetetraacetate.

[0033] The method for preparing the β-cyclodextrin containing the plant-based deodorizing extract includes the following steps: dissolving β-cyclodextrin in deionized water at 58°C to form a saturated solution; slowly adding the plant-based deodorizing extract dropwise to the above cyclodextrin aqueous solution at a core-to-wall ratio of 7:1, with the addition time controlled at 30 min; stirring and incorporating at a constant temperature and in a sealed environment for 2.5 h; naturally cooling to room temperature; allowing to stand and age for 10 h to allow the inclusion complex to fully crystallize and precipitate; filtering, washing the filter cake with deionized water, vacuum drying at 40°C, and pulverizing through an 80-mesh sieve to obtain the β-cyclodextrin inclusion complex powder containing the plant-based deodorizing extract.

[0034] The preparation method of the plant-based deodorizing extract includes the following steps: mixing fresh and dried peppermint, mugwort, rosemary, and tea tree, pulverizing them, and passing them through a 20-mesh sieve to obtain a plant mixture powder; adding 6 times the mass of deionized water to the plant mixture powder, soaking for 30 minutes, and then heating to 95°C and decocting for 2 hours; coarsely filtering and centrifuging the extract to remove solid residues, and collecting the supernatant; passing the supernatant through rotary evaporation and microporous membrane filtration to obtain the plant-based deodorizing extract; the mass ratio of fresh and dried peppermint, mugwort, rosemary, and tea tree is 2:1:3:3; the degree of substitution of the chitosan quaternary ammonium salt is 90%, and the number average molecular weight is 100,000; the plant polysaccharide is trehalose.

[0035] A method for preparing the high-efficiency composite environmentally friendly deodorizing and passivating cleaning agent includes the following steps: mixing each component evenly according to the weight parts, and letting it stand for 2 hours to obtain the high-efficiency composite environmentally friendly deodorizing and passivating cleaning agent.

[0036] Example 2

[0037] A highly efficient, composite, environmentally friendly deodorizing and passivating cleaning agent, by weight percentage, comprises the following components: 9wt% slow-release oxidant, 4wt% dispersant, 3wt% penetrant, 1.5wt% corrosion inhibitor, 3.5wt% activator, 3.5wt% auxiliary passivator, 8.5wt% composite deodorizer, 1.5wt% synergist, 0.7wt% β-cyclodextrin containing plant-based deodorizing extract, 2wt% chitosan quaternary ammonium salt, 0.9wt% plant polysaccharide, with the balance being deionized water; the slow-release oxidant is a low-temperature co-soluble composite salt of sodium percarbonate and sodium gluconate; the corrosion inhibitor includes 3-mercaptopropyltriethoxysilane; the composite deodorizer is a compound of ultrafine sodium silicate, hydroxyethylidene diphosphonic acid, and microbial agent in a weight ratio of 3.5:1.5:0.15.

[0038] The preparation method of the slow-release oxidant includes the following steps: adding deionized water to a reaction vessel, heating to 42°C, adding sodium percarbonate and sodium gluconate, stirring to dissolve, adjusting the pH to 6.6, keeping warm for 32 minutes, cooling to crystallize, drying and pulverizing to obtain the slow-release oxidant; the molar ratio of sodium percarbonate, sodium gluconate and deionized water is 1:0.9:7; the dispersant is sodium lignosulfonate; the penetrant is fatty alcohol polyoxyethylene ether; the corrosion inhibitor is a compound of sodium sarcosinate, 2-mercaptobenzimidazole and 3-mercaptopropyltriethoxysilane in a mass ratio of 1:1.3:0.9; the activator is ammonium sulfate; and the auxiliary passivating agent is tetramethylolphosphine sulfate.

[0039] The ultrafine sodium silicate has a particle size of 250 mesh; the microbial agent is an effective live bacteria powder, formulated by compounding Bacillus licheniformis AS 1.813 and Bacillus subtilis CGMCC 1.3358 at a dry basis mass ratio of 1.5:1; wherein the effective live count of Bacillus licheniformis is ≥2.0 × 10⁻⁶. 9 CFU / g, effective viable count of Bacillus subtilis ≥2.0×10⁻⁶ 9 CFU / g; the synergist is disodium ethylenediaminetetraacetate.

[0040] The method for preparing the β-cyclodextrin containing the plant-based deodorizing extract includes the following steps: dissolving β-cyclodextrin in deionized water at 59°C to form a saturated solution; slowly adding the plant-based deodorizing extract dropwise to the above cyclodextrin aqueous solution at a core-to-wall ratio of 7.3:1, with the addition time controlled at 32 min; stirring and incorporating at a constant temperature and in a sealed environment for 2.8 h; naturally cooling to room temperature; allowing to stand and age for 12 h to allow the inclusion complex to fully crystallize and precipitate; filtering, washing the filter cake with deionized water, vacuum drying at 43°C, and pulverizing through an 85-mesh sieve to obtain the β-cyclodextrin inclusion complex powder containing the plant-based deodorizing extract.

[0041] The preparation method of the plant-based deodorizing extract includes the following steps: mixing fresh and dried peppermint, mugwort, rosemary, and tea tree, pulverizing them, and passing them through a 25-mesh sieve to obtain a plant mixture powder; adding 7 times the mass of deionized water to the plant mixture powder, soaking for 40 minutes, and then heating to 97°C and decocting for 2.5 hours; coarsely filtering and centrifuging to remove solid residues from the extract, and collecting the supernatant; passing the supernatant through rotary evaporation and microporous membrane filtration to obtain the plant-based deodorizing extract; the mass ratio of fresh and dried peppermint, mugwort, rosemary, and tea tree is 2.5:1.5:3.5:3; the degree of substitution of the chitosan quaternary ammonium salt is 90%, and the number average molecular weight is 100,000; the plant polysaccharide is trehalose.

[0042] A method for preparing the high-efficiency composite environmentally friendly deodorizing and passivating cleaning agent includes the following steps: mixing each component evenly according to the weight parts, and letting it stand for 2.5 hours to obtain the high-efficiency composite environmentally friendly deodorizing and passivating cleaning agent.

[0043] Example 3

[0044] A highly efficient, composite, environmentally friendly deodorizing and passivating cleaning agent, by weight percentage, comprises the following components: 11 wt% slow-release oxidant, 4.5 wt% dispersant, 3.5 wt% penetrant, 1.8 wt% corrosion inhibitor, 4 wt% activator, 4 wt% auxiliary passivating agent, 9 wt% composite deodorizer, 2 wt% synergist, 0.9 wt% β-cyclodextrin containing plant-based deodorizing extract, 2.5 wt% chitosan quaternary ammonium salt, 1 wt% plant polysaccharide, with the balance being deionized water; the slow-release oxidant is a low-temperature co-soluble composite salt of sodium percarbonate and sodium gluconate; the corrosion inhibitor includes 3-mercaptopropyltriethoxysilane; the composite deodorizer is a compound of ultrafine sodium silicate, hydroxyethylidene diphosphonic acid, and microbial agent in a weight ratio of 4:2:0.2.

[0045] The preparation method of the slow-release oxidant includes the following steps: adding deionized water to a reaction vessel, heating to 43°C, adding sodium percarbonate and sodium gluconate, stirring to dissolve, adjusting the pH to 6.8, keeping warm for 35 minutes, cooling to crystallize, drying and pulverizing to obtain the slow-release oxidant; the molar ratio of sodium percarbonate, sodium gluconate and deionized water is 1:1:8; the dispersant is sodium lignosulfonate; the penetrant is fatty alcohol polyoxyethylene ether; the corrosion inhibitor is sodium sarcosinate, 2-mercaptobenzimidazole and 3-mercaptopropyltriethoxysilane compounded in a mass ratio of 1:1.5:1; the activator is ammonium nitrate; and the auxiliary passivating agent is tetramethylphosphoric acid sulfate.

[0046] The ultrafine sodium silicate has a particle size of 280 mesh; the microbial agent is an effective live bacteria powder, formulated by compounding Bacillus licheniformis AS 1.813 and Bacillus subtilis CGMCC 1.3358 at a dry basis mass ratio of 2:1; wherein the effective live count of Bacillus licheniformis is ≥2.0 × 10⁻⁶. 9 CFU / g, effective viable count of Bacillus subtilis ≥2.0×10⁻⁶ 9 CFU / g; the synergist is disodium ethylenediaminetetraacetate.

[0047] The method for preparing the β-cyclodextrin containing the plant-based deodorizing extract includes the following steps: dissolving β-cyclodextrin in deionized water at 60°C to form a saturated solution; slowly adding the plant-based deodorizing extract dropwise to the above cyclodextrin aqueous solution at a core-to-wall ratio of 7.5:1, with the addition time controlled at 35 min; stirring and incorporating at a constant temperature and in a sealed environment for 3 h; naturally cooling to room temperature; allowing to stand and age for 12 h to allow the inclusion complex to fully crystallize and precipitate; filtering, washing the filter cake with deionized water, vacuum drying at 45°C, and pulverizing through a 90-mesh sieve to obtain the β-cyclodextrin inclusion complex powder containing the plant-based deodorizing extract.

[0048] The preparation method of the plant-based deodorizing extract includes the following steps: mixing fresh and dried peppermint, mugwort, rosemary, and tea tree, pulverizing them, and passing them through a 30-mesh sieve to obtain a plant mixture powder; adding 8 times the mass of deionized water to the plant mixture powder, soaking for 45 minutes, and then heating to 98°C and decocting for 3 hours; the extract is coarsely filtered and centrifuged to remove solid residues, and the supernatant is collected; the supernatant is then subjected to rotary evaporation and fine filtration through a microporous membrane to obtain the plant-based deodorizing extract; the mass ratio of fresh and dried peppermint, mugwort, rosemary, and tea tree is 3:2:4:3; the degree of substitution of the chitosan quaternary ammonium salt is 90%, and the number average molecular weight is 100,000; the plant polysaccharide is trehalose.

[0049] A method for preparing the high-efficiency composite environmentally friendly deodorizing and passivating cleaning agent includes the following steps: mixing each component evenly according to the weight parts, and letting it stand for 3 hours to mature, thereby obtaining the high-efficiency composite environmentally friendly deodorizing and passivating cleaning agent.

[0050] Example 4

[0051] A highly efficient, composite, environmentally friendly deodorizing and passivating cleaning agent, by weight percentage, comprises the following components: 13wt% slow-release oxidant, 5.5wt% dispersant, 4.5wt% penetrant, 2.3wt% corrosion inhibitor, 4.5wt% activator, 4.5wt% auxiliary passivating agent, 9.5wt% composite deodorizer, 2.5wt% synergist, 1.1wt% β-cyclodextrin containing plant-based deodorizing extract, 2.8wt% chitosan quaternary ammonium salt, 1.1wt% plant polysaccharide, and the balance being deionized water; the slow-release oxidant is a low-temperature co-soluble composite salt of sodium percarbonate and sodium gluconate; the corrosion inhibitor includes 3-mercaptopropyltriethoxysilane; the composite deodorizer is a compound of ultrafine sodium silicate, hydroxyethylidene diphosphonic acid, and microbial agent in a weight ratio of 4.5:2.5:0.25.

[0052] The preparation method of the slow-release oxidant includes the following steps: adding deionized water to a reaction vessel, heating to 44°C, adding sodium percarbonate and sodium gluconate, stirring to dissolve, adjusting the pH to 6.9, keeping warm for 38 minutes, cooling to crystallize, drying and pulverizing to obtain the slow-release oxidant; the molar ratio of sodium percarbonate, sodium gluconate and deionized water is 1:1.1:9; the dispersant is sodium lignosulfonate; the penetrant is fatty alcohol polyoxyethylene ether; the corrosion inhibitor is a compound of sodium sarcosinate, 2-mercaptobenzimidazole and 3-mercaptopropyltriethoxysilane in a mass ratio of 1:1.8:1.1; the activator is ammonium nitrate; and the auxiliary passivating agent is tetramethylphosphoric acid sulfate.

[0053] The ultrafine sodium silicate has a particle size of 200-325 mesh; the microbial agent is an effective live bacteria powder, formulated by compounding Bacillus licheniformis AS 1.813 and Bacillus subtilis CGMCC 1.3358 at a dry basis mass ratio of 2.5:1; wherein the effective live count of Bacillus licheniformis is ≥2.0×10⁻⁶. 9 CFU / g, effective viable count of Bacillus subtilis ≥2.0×10⁻⁶ 9 CFU / g; the synergist is a mixture of disodium ethylenediaminetetraacetate and potassium pyrophosphate in a mass ratio of 1:1.

[0054] The method for preparing the β-cyclodextrin containing the plant-based deodorizing extract includes the following steps: dissolving β-cyclodextrin in deionized water at 61°C to form a saturated solution; slowly adding the plant-based deodorizing extract dropwise to the above cyclodextrin aqueous solution at a core-to-wall ratio of 7.8:1, with the addition time controlled at 38 min; stirring and incorporating at a constant temperature and in a sealed environment for 3.3 h; naturally cooling to room temperature; allowing to stand and age for 13 h to allow the inclusion complex to fully crystallize and precipitate; filtering, washing the filter cake with deionized water, vacuum drying at 48°C, and pulverizing through a 95-mesh sieve to obtain the β-cyclodextrin inclusion complex powder containing the plant-based deodorizing extract.

[0055] The preparation method of the plant-based deodorizing extract includes the following steps: mixing fresh and dried peppermint, mugwort, rosemary, and tea tree, pulverizing them, and passing them through a 35-mesh sieve to obtain a plant mixture powder; adding 9 times the mass of deionized water to the plant mixture powder, soaking for 55 minutes, and then heating to 99°C and decocting for 3.5 hours; coarsely filtering and centrifuging the extract to remove solid residues, and collecting the supernatant; passing the supernatant through rotary evaporation and microporous membrane filtration to obtain the plant-based deodorizing extract; the mass ratio of fresh and dried peppermint, mugwort, rosemary, and tea tree is 3.5:2.5:4.5:3; the degree of substitution of the chitosan quaternary ammonium salt is 90%, and the number average molecular weight is 100,000; the plant polysaccharide is trehalose.

[0056] A method for preparing the high-efficiency composite environmentally friendly deodorizing and passivating cleaning agent includes the following steps: mixing each component evenly according to the weight parts, and letting it stand for 3.5 hours to obtain the high-efficiency composite environmentally friendly deodorizing and passivating cleaning agent.

[0057] Example 5

[0058] A highly efficient, composite, environmentally friendly deodorizing and passivating cleaning agent, by weight percentage, comprises the following components: 14wt% slow-release oxidant, 6wt% dispersant, 5wt% penetrant, 2.5wt% corrosion inhibitor, 5wt% activator, 5wt% auxiliary passivating agent, 10wt% composite deodorant, 3wt% synergist, 1.2wt% β-cyclodextrin containing plant-based deodorizing extract, 3wt% chitosan quaternary ammonium salt, 1.2wt% plant polysaccharide, and the balance being deionized water; the slow-release oxidant is a low-temperature co-soluble composite salt of sodium percarbonate and sodium gluconate; the corrosion inhibitor includes 3-mercaptopropyltriethoxysilane; the composite deodorant is a mixture of ultrafine sodium silicate, hydroxyethylidene diphosphonic acid, and microbial agent in a weight ratio of 5:3:0.3.

[0059] The preparation method of the slow-release oxidant includes the following steps: adding deionized water to a reaction vessel, heating to 45°C, adding sodium percarbonate and sodium gluconate, stirring to dissolve, adjusting the pH to 7.0, keeping warm for 40 minutes, cooling to crystallize, drying and pulverizing to obtain the slow-release oxidant; the molar ratio of sodium percarbonate, sodium gluconate and deionized water is 1:1.2:10; the dispersant is sodium lignosulfonate; the penetrant is fatty alcohol polyoxyethylene ether; the corrosion inhibitor is a compound of sodium sarcosinate, 2-mercaptobenzimidazole and 3-mercaptopropyltriethoxysilane in a mass ratio of 1:2:1.2; the activator is ammonium nitrate; and the auxiliary passivating agent is tetramethylphosphoric acid sulfate.

[0060] The ultrafine sodium silicate has a particle size of 325 mesh; the microbial agent is an effective live bacteria powder, formulated by compounding Bacillus licheniformis AS 1.813 and Bacillus subtilis CGMCC 1.3358 at a dry basis mass ratio of 3:1; wherein the effective live count of Bacillus licheniformis is ≥2.0 × 10⁻⁶. 9 CFU / g, effective viable count of Bacillus subtilis ≥2.0×10⁻⁶ 9 CFU / g; the synergist is disodium ethylenediaminetetraacetate.

[0061] The method for preparing the β-cyclodextrin containing the plant-based deodorizing extract includes the following steps: dissolving β-cyclodextrin in deionized water at 62°C to form a saturated solution; slowly adding the plant-based deodorizing extract dropwise to the above cyclodextrin aqueous solution at a core-to-wall ratio of 8:1, with the addition time controlled at 40 min; stirring and incorporating at a constant temperature and in a sealed environment for 3.5 h; naturally cooling to room temperature; allowing to stand and age for 14 h to allow the inclusion complex to fully crystallize and precipitate; filtering, washing the filter cake with deionized water, vacuum drying at 50°C, and pulverizing through a 100-mesh sieve to obtain the β-cyclodextrin inclusion complex powder containing the plant-based deodorizing extract.

[0062] The preparation method of the plant-based deodorizing extract includes the following steps: mixing fresh and dried peppermint, mugwort, rosemary, and tea tree, pulverizing them, and passing them through a 40-mesh sieve to obtain a plant mixture powder; adding 10 times the mass of deionized water to the plant mixture powder, soaking for 60 minutes, and then decocting at 100℃ for 4 hours; the extract is coarsely filtered and centrifuged to remove solid residues, and the supernatant is collected; the supernatant is then subjected to rotary evaporation and fine filtration through a microporous membrane to obtain the plant-based deodorizing extract; the mass ratio of fresh and dried peppermint, mugwort, rosemary, and tea tree is 4:3:5:3; the degree of substitution of the chitosan quaternary ammonium salt is 90%, and the number average molecular weight is 100,000; the plant polysaccharide is trehalose.

[0063] A method for preparing the high-efficiency composite environmentally friendly deodorizing and passivating cleaning agent includes the following steps: mixing each component evenly according to the weight parts, and letting it stand for 4 hours to obtain the high-efficiency composite environmentally friendly deodorizing and passivating cleaning agent.

[0064] Comparative Example 1 A highly efficient, composite, environmentally friendly deodorizing and passivating cleaning agent and its preparation method are basically the same as in Example 5, except that an equal amount of sodium percarbonate is used instead of the slow-release oxidant.

[0065] Comparative Example 2 A highly efficient, composite, environmentally friendly deodorizing and passivating cleaning agent and its preparation method are basically the same as in Example 5, except that an equal amount of hydroxyethylidene diphosphonic acid is used instead of the microbial agent.

[0066] Comparative Example 3 A highly efficient, composite, environmentally friendly deodorizing and passivating cleaning agent and its preparation method are basically the same as in Example 5, except that an equal amount of microbial agent is used instead of hydroxyethylidene diphosphonic acid.

[0067] Comparative Example 4 A highly efficient composite environmentally friendly deodorizing and passivating cleaning agent and its preparation method are basically the same as those in Example 5, except that an equal amount of 2-mercaptobenzimidazole is used instead of 3-mercaptopropyltriethoxysilane.

[0068] Comparative Example 5 A highly efficient, composite, environmentally friendly deodorizing and passivating cleaning agent and its preparation method are basically the same as in Example 5, except that an equal amount of chitosan quaternary ammonium salt is used instead of plant polysaccharides.

[0069] Comparative Example 6 A highly efficient, composite, environmentally friendly deodorizing and passivating cleaning agent and its preparation method are basically the same as in Example 5, except that an equal amount of plant polysaccharides are used instead of chitosan quaternary ammonium salt.

[0070] Experimental data verification The experimental method is as follows: (1) Deodorization performance test: Take a cleaning agent sample and prepare a test solution at 5% of the mass of the cleaning agent stock solution (i.e., 5g of cleaning agent stock solution is contained in every 100g of test solution, and the rest is water). Place the solution in a sealed container and pass in a 1000mg / m³ concentration of water. 3 H2S gas 500mg / m³ 3 After the methanethiol gas was stirred at a constant temperature for 30 minutes, the concentration of the remaining odorous gas was measured using a gas detection instrument, and the deodorization rate was calculated.

[0071] (2) Cleaning performance test: Prepare ferrous sulfide standard scale blocks. Take analytical grade ferrous sulfide powder (particle size 200 mesh), add a small amount of deionized water to make a paste, put it into a mold (size 20mm×20mm×10mm), dry it in a constant temperature oven at 105℃ for 2 hours until constant weight, take it out and cool it to room temperature before demolding to obtain ferrous sulfide standard scale blocks (single block mass about 5g). Weigh and record the mass of each scale block (accurate to 0.0001g); prepare test solution (i.e., 100g test solution) according to the mass of the cleaning agent stock solution accounting for 5% of the total mass of the test solution. The test solution contains 5g of cleaning agent stock solution, the rest being water. Take 150mL of the test solution and place it in a 250mL beaker. Add one prepared ferrous sulfide standard scale block and place the beaker in a constant temperature water bath. Control the temperature at 40℃ and the stirring speed at 150r / min, and stir at this temperature for 2 hours. After stirring, filter the solution with qualitative filter paper. Gently rinse the remaining scale block three times with deionized water to remove the test solution adhering to the surface. Place the scale block in a 105℃ constant temperature oven to dry to constant weight. After cooling to room temperature, weigh and record the weight. Calculate the cleaning rate based on the weight of the scale block before and after cleaning.

[0072] (3) Corrosion inhibition performance test: The weight loss method was used for testing. Q235 carbon steel test pieces (50mm×25mm×2mm) were selected and polished stepwise with 400-grit and 800-grit sandpaper until the surface was smooth and free of scratches. They were then rinsed with deionized water, dehydrated with anhydrous ethanol, and dried in a 105℃ constant temperature oven for 2 hours until constant weight. After cooling to room temperature, they were weighed and the initial mass of the test piece was recorded (accurate to 0.0001g). The test solution was prepared according to the mass of the cleaning agent stock solution accounting for 5% of the total mass of the test solution (i.e., 100g of test solution contains 5% of the total mass of the test solution). 5g of cleaning agent concentrate (the rest is water). Take 200mL of test solution and place it in a 500mL beaker. Completely immerse the weighed test piece in the test solution, seal the beaker to prevent the test solution from evaporating, and soak at room temperature (25±2℃) for 24 hours. After soaking, remove the test piece, rinse the surface with deionized water to remove residual test solution and adhering substances, then dehydrate it with anhydrous ethanol, and dry it in a 105℃ constant temperature oven for 2 hours until constant weight. After cooling to room temperature, weigh the test piece and record its mass after soaking. Calculate the corrosion rate based on the difference in mass of the test piece before and after soaking.

[0073] (4) System stability test: Take 100g of each cleaning agent sample, place them in sealed glass containers, mark them, and let them stand at room temperature (25℃) for 30 days. Record whether there is layering, precipitation, discoloration, or odor. If there is no layering, precipitation, discoloration, or odor, the system stability is passed; otherwise, it is not passed.

[0074] The experimental results are shown in Table 1.

[0075] As can be seen from the test results in Table 1, the deodorizing and passivating cleaning agent obtained by compounding in Example 5 of the present invention has the best comprehensive performance. Its deodorization rate reaches 99.55%, the cleaning rate of ferrous sulfide scale reaches 97.28%, the corrosion rate of carbon steel is as low as 0.0042 mm / a, and the stability of the system at room temperature is qualified. Compared with the various proportions of replacing the slow-release oxidant, the composite deodorizer component, the silane corrosion inhibitor, and the chitosan quaternary ammonium salt and plant polysaccharide respectively, Example 5 has significant advantages in deodorization and decontamination ability, metal corrosion inhibition and protection effect, and system storage stability. Among them, the slow-release oxidant has a particularly prominent effect on cleaning and deodorization performance, the silane compound corrosion inhibitor has a particularly prominent effect on carbon steel corrosion protection performance, and the polymer polysaccharide compound system has a particularly prominent effect on product stability. This fully demonstrates that the core components in the formula of the present invention are scientifically matched and synergistically enhanced, and none of them can be omitted.

[0076] Table 1 Performance test results of high-efficiency composite environmentally friendly deodorizing and passivating cleaning agent The above embodiments are only for illustrating the technical concept and features of the present invention. Their purpose is to enable those skilled in the art to understand the content of the present invention and implement it accordingly. They should not be used to limit the scope of protection of the present invention. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A high-efficiency, composite, environmentally friendly deodorizing and passivating cleaning agent, characterized in that, The product, by weight percentage, comprises the following components: 7-14 wt% slow-release oxidant, 3-6 wt% dispersant, 2-5 wt% penetrant, 0.8-2.5 wt% corrosion inhibitor, 3-5 wt% activator, 3-5 wt% auxiliary passivator, 8-10 wt% composite deodorant, 1-3 wt% synergist, 0.5-1.2 wt% β-cyclodextrin containing plant-based deodorizing extract, 1.5-3 wt% chitosan quaternary ammonium salt, 0.8-1.2 wt% plant polysaccharide, with the balance being deionized water; the slow-release oxidant is a low-temperature co-soluble composite salt of sodium percarbonate and sodium gluconate; the corrosion inhibitor includes 3-mercaptopropyltriethoxysilane; the composite deodorant is a mixture of ultrafine sodium silicate, hydroxyethylidene diphosphonic acid, and microbial agent in a weight ratio of (3-5):(1-3):(0.1-0.3).

2. The high-efficiency composite environmentally friendly deodorizing and passivating cleaning agent according to claim 1, characterized in that, The method for preparing the slow-release oxidant includes the following steps: adding deionized water to a reaction vessel, heating to 40-45°C, adding sodium percarbonate and sodium gluconate, stirring to dissolve, adjusting the pH to 6.5-7.0, keeping warm for 30-40 minutes, cooling to crystallize, drying and pulverizing to obtain the slow-release oxidant; the molar ratio of sodium percarbonate, sodium gluconate and deionized water is 1:(0.8-1.2):(6-10).

3. The high-efficiency composite environmentally friendly deodorizing and passivating cleaning agent according to claim 1, characterized in that, The dispersant is sodium lignosulfonate; the penetrant is fatty alcohol polyoxyethylene ether.

4. The high-efficiency composite environmentally friendly deodorizing and passivating cleaning agent according to claim 1, characterized in that, The corrosion inhibitor is a compound of sodium sarcosinate, 2-mercaptobenzimidazole, and 3-mercaptopropyltriethoxysilane in a mass ratio of 1:(1-2):(0.8-1.2).

5. The high-efficiency composite environmentally friendly deodorizing and passivating cleaning agent according to claim 1, characterized in that, The activator is at least one of ammonium nitrate and ammonium sulfate; the auxiliary passivating agent is tetrahydroxymethylphosphoric acid.

6. The high-efficiency composite environmentally friendly deodorizing and passivating cleaning agent according to claim 1, characterized in that, The ultrafine sodium silicate has a particle size of 200-325 mesh; the microbial agent is an effective live bacteria powder, formulated by compounding Bacillus licheniformis AS 1.813 and Bacillus subtilis CGMCC 1.3358 at a dry basis mass ratio of (1-3):1; wherein the effective live count of Bacillus licheniformis is ≥2.0×10⁻⁶. 9 CFU / g, effective viable count of Bacillus subtilis ≥2.0×10⁻⁶ 9 CFU / g; the synergist is at least one of disodium ethylenediaminetetraacetate and potassium pyrophosphate.

7. The high-efficiency composite environmentally friendly deodorizing and passivating cleaning agent according to claim 1, characterized in that, The method for preparing the β-cyclodextrin containing the plant-based deodorizing extract includes the following steps: dissolving β-cyclodextrin in deionized water at 58-62℃ to form a saturated solution; slowly adding the plant-based deodorizing extract dropwise to the above cyclodextrin aqueous solution at a core-to-wall ratio of (7-8):1, with the addition time controlled at 30-40 min; stirring and incorporating at a constant temperature and in a sealed environment for 2.5-3.5 h; naturally cooling to room temperature; allowing to stand and age for 10-14 h to allow the inclusion complex to fully crystallize and precipitate; filtering, washing the filter cake with deionized water, vacuum drying at a low temperature of 40-50℃, and pulverizing through an 80-100 mesh sieve to obtain the β-cyclodextrin inclusion complex powder containing the plant-based deodorizing extract.

8. The high-efficiency composite environmentally friendly deodorizing and passivating cleaning agent according to claim 7, characterized in that, The preparation method of the plant-based deodorizing extract includes the following steps: mixing fresh and dried peppermint, mugwort, rosemary, and tea tree, pulverizing them, and passing them through a 20-40 mesh sieve to obtain a plant mixture powder; adding 6-10 times the mass of deionized water to the plant mixture powder, soaking for 30-60 minutes, and then heating to 95-100℃ and decocting for 2-4 hours; filtering the extract coarsely and centrifuging to remove solid residues, and collecting the supernatant; passing the supernatant through rotary evaporation and fine filtration through a microporous membrane to obtain the plant-based deodorizing extract; the mass ratio of fresh and dried peppermint, mugwort, rosemary, and tea tree is (2-4):(1-3):(3-5):

3.

9. The high-efficiency composite environmentally friendly deodorizing and passivating cleaning agent according to claim 1, characterized in that, The degree of substitution of the chitosan quaternary ammonium salt is 90%, and the number average molecular weight is 100,000; the plant polysaccharide is trehalose.

10. A method for preparing a high-efficiency composite environmentally friendly deodorizing and passivating cleaning agent according to any one of claims 1-9, characterized in that, The process includes the following steps: after mixing each component evenly according to the weight parts, let it stand for 2-4 hours to mature, and obtain a high-efficiency composite environmentally friendly deodorizing and passivating cleaning agent.

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