A kind of calcined coke wastewater demulsifier and its preparation method

Abstract

The present application relates to demulsifier production technical field, especially a kind of calcined coke sewage demulsifier and preparation method thereof, including the following weight percentage components: 10-30% modified amide demulsifying main agent, 10-20% cationic organic matter, 1-3% heavy metal capture agent, 1-3% defoaming agent and the balance water;The synthetic components of the modified amide demulsifying main agent include starter, catalyst, chain extender, and the modified amide demulsifying main agent is prepared by the reaction of the starter, the catalyst and ethylene oxide.The calcined coke sewage demulsifier prepared in the present application is an environmentally friendly raw material, with low cost, high safety in production and use, fast demulsification speed, no influence on the stability of subsequent biochemical system, and reduction of metal ions in sewage;The cellulose is chain-extended and modified based on the purpose of optimizing the demulsification performance of calcined coke sewage demulsifier.First, methyl alcohol group is introduced by using ethylene oxide, then the product is amidated by using low-cost urea as chain extender to obtain demulsifying main agent.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of demulsifier production, and particularly relates to a calcined coke wastewater demulsifier and a preparation method thereof. BACKGROUND

[0002] The demulsifier destroys the emulsion film formed in the oil-water emulsion, and the demulsification process of the demulsifier is a process in which the demulsifier molecules penetrate and adhere to the interface of the emulsion droplets to replace the natural emulsifiers (machine slag, coke particles, ash) and destroy the surface film. The demulsifier releases the water or oil wrapped in the film, and the water droplets or oil droplets are gathered and become larger, so that the oil-water two phases are separated.

[0003] The demulsifier is also an excellent viscosity reducer when separating oil and water, which can generate a film on the surface of the oil droplets, reduce the surface tension of the oil droplets, greatly reduce the viscosity of the oil droplets, and enhance the flowability of the oil droplets, so that the oil droplets are not easy to adhere to the equipment. The demulsifier also has a certain purification effect, and the turbidity of the water quality is obviously reduced.

[0004] The calcined coke wastewater demulsifier is mainly used for demulsification and sedimentation of wastewater generated by high-temperature calcination of petroleum coke (green coke), and is mainly used in the aluminum electrolysis, steel, titanium sponge and other industries. When the cooling flue gas is used, a part of the coke oil and light oil will be brought out. Since the circulating water of the cooling flue gas uses the wastewater of the front-end electrolysis process, the water also contains a certain amount of salt, which affects the biochemical treatment of the wastewater or the formation of the filter cake, so it is necessary to demulsify the part of the oily wastewater to separate the oil and water and purify the wastewater.

[0005] The existing demulsification methods include physical method, chemical method or a combination of the two methods. At present, most of the demulsifiers used in China are nonionic demulsifiers of polyether or modified polyether.

[0006] According to the search, the patent with the publication number CN104291412A discloses that a polyepoxy chloropropane is obtained by self-polymerization of epoxy chloropropane as a raw material, and then reacts with an organic amine and carbon disulfide to obtain a demulsifier. The raw material of the reaction is a gas, and carbon disulfide is explosive, so the storage and application safety requirements are relatively high, and enterprises other than the enterprises allowed to use dangerous chemicals are not allowed to produce.

[0007] Therefore, it is necessary to develop a demulsifier with fast demulsification speed, good water purification effect and suitable for the characteristics of calcined coke wastewater, to purify the water quality of the wastewater, separate the oil and water, and solve the problem of non-formation of the filter cake at the back end. SUMMARY

[0008] The present application is to solve one of the above technical problems, the technical solution is: a kind of calcined coke wastewater demulsifier, including the following weight percentage components: 10%-30% of modified amide demulsification main agent, 10%-20% of cationic organic matter, 1%-3% of heavy metal capture agent, 1%-3% defoaming agent and the rest water;The synthesis of the modified amide demulsification main agent includes starter, catalyst, chain extender, and the modified amide demulsification main agent is prepared by the reaction of the starter, catalyst and ethylene oxide.

[0009] On the basis of any one of the above technical solutions, further optimization is: the starter is cellulose;The catalyst is organic or inorganic catalyst;The chain extender is urea.

[0010] On the basis of any one of the above technical solutions, further optimization is: the chemical structural formula of the modified amide demulsification main agent is: .

[0012] On the basis of any one of the above technical solutions, further optimization is: the preparation method of the modified amide demulsification main agent is:

[0013] 1) cellulose is used as raw material, and is reacted with ethylene oxide under alkaline conditions to obtain a first reaction intermediate, and the specific reaction formula is as follows: .

[0014] 2) an excess of urea solution is added to the first reaction intermediate obtained in step 1), and is catalyzed to react at a reaction temperature of 90-120 DEG C for 2-4 hours to obtain the final product modified amide demulsifier, and the specific reaction formula is as follows:

[0015] .

[0016] On the basis of any one of the above technical solutions, further optimization is: the organic or inorganic catalyst in step 2) is sodium methoxide or sodium sulfate.

[0017] On the basis of any one of the above technical solutions, further optimization is: the reaction temperature in step 2) is about 100 DEG C.

[0018] On the basis of any one of the above technical solutions, further optimization is: the reaction time in step 2) is 3 hours.

[0019] On the basis of any one of the above technical solutions, further optimization is: the cationic organic matter is one or both of tetramethylammonium chloride and polyamine.

[0020] On the basis of any one of the preceding technical solutions, further optimization is that the heavy metal capturing agent is one or both of TMT or sulfide.

[0021] On the basis of any one of the preceding technical solutions, further optimization is that the defoaming agent is one or both of a high-carbon alcohol defoaming agent and a polyether defoaming agent.

[0022] The application also provides a method for preparing the calcined coke wastewater demulsifier, characterized in that the method comprises the following steps:

[0023] S1, preparation of a modified amide demulsifying main agent:

[0024] 1) using cellulose as a raw material, reacting with ethylene oxide under alkaline conditions to obtain a first reaction intermediate until the hydroxyl peak at 3200-3600 cm-1 disappears, thereby obtaining the first reaction intermediate;

[0025] 2) adding a urea solution dropwise to the substance obtained in step 1) to obtain a macromolecular substance capped with an amide group, the reaction temperature is 90-120 DEG C, the reaction time is 2-4 hours, and the final product, the modified amide demulsifier, is obtained;

[0026] S2, a certain mass of deionized water or pure water is put into a mixing kettle, and the modified amide demulsifying main agent, the cationic organic substance, the heavy metal capturing agent, and the defoaming agent are sequentially put into the mixing kettle, and stirred for 30-40 min until the system is uniform, thereby obtaining the calcined coke wastewater demulsifier.

[0027] Compared with the prior art, the application has the following beneficial effects:

[0028] 1) The calcined coke wastewater demulsifier prepared by the application is made of environmentally friendly raw materials, has low cost, high safety in production and use, fast demulsification speed, does not affect the stability of the subsequent biochemical system, and reduces metal ions in wastewater.

[0029] 2) The calcined coke wastewater demulsifier of the application is based on the purpose of optimizing the demulsification performance, and the cellulose is chain-extended and modified. First, methyl alcohol groups are introduced by using ethylene oxide, and then a low-cost urea is used as a chain extender to perform amide group modification to obtain a demulsifying main agent.

[0030] 3) The demulsifying main agent is a high-molecular-weight substance having both hydrophilic and lipophilic properties, low surface tension, and can quickly break the oil-water interface film, and the amide groups can combine with small oil droplets and suspended solids in water to form bridges to accelerate sedimentation, thereby achieving excellent oil-water separation and solid-liquid separation effects. Then, the demulsifying main agent is coordinated with other additives to achieve the purpose of gathering oil, water and solids separately and quickly separating the three phases.

[0031] The preparation method of the calcined coke wastewater demulsifier disclosed by the application is based on the composition of each component, corresponding process steps and the adding sequence of each component are formulated, and the demulsifier with stable system is obtained by compounding. DETAILED DESCRIPTION

[0032] The embodiments of the technical scheme of the application will be described in detail below. The following embodiments are only used to more clearly illustrate the technical scheme of the application, and therefore only serve as examples, and cannot limit the protection scope of the application.

[0033] In order to make the preparation method of the application more clear, the effect and the advantages of the product are more clear, the technical scheme of the application will be described in detail below. Next, the embodiments described are only a part of the embodiments of the application, not all the embodiments. The embodiments are helpful to interpret and define the inventive content of the application, and other embodiments obtained by other researchers without making a more outstanding creative effort belong to the scope of protection of the application.

[0034] Embodiment 1: The embodiment discloses a calcined coke wastewater demulsifier, which is prepared from the following components:

[0035] A steel plant wastewater demulsifier, characterized in that the raw materials include the following components in percentage by weight: 30% of a modified amide demulsifying main agent, 15% of a cationic organic matter, 3% of a heavy metal capturing agent, 1% of a defoaming agent, and the balance of water; the wastewater demulsifier product is obtained after stirring for more than 40 minutes.

[0036] The wastewater of a certain steel plant has a layer of floating oil on the surface, the iron content in the water is 200-500 mg / L, and it is difficult to make the iron ions settle by using a traditional settlement flocculant, the floating oil is thicker and thicker, cannot enter the biochemical system, and cannot meet the drainage requirements, thereby affecting the normal operation of the enterprise.

[0037] After 300 PPM of the demulsifier of the application is added, the surface floating oil is eliminated, the iron ions are reduced to 90% by the action of the agent, and the water quality meets the standards after entering the subsequent treatment process.

[0038] Embodiment 2: The embodiment discloses a calcined coke wastewater demulsifier, which is prepared from the following components:

[0039] A calcined coke wastewater demulsifier, characterized in that the raw materials include the following components in percentage by weight: 30% of a modified amide demulsifying main agent, 15% of a cationic organic matter, 1% of a heavy metal capturing agent, 1% of a defoaming agent, and the balance of water; the wastewater demulsifier product is obtained after stirring for more than 40 minutes.

[0040] The wastewater for washing impellers of a certain titanium sponge production plant contains petroleum coke, the salt content is as high as 52%, it is difficult to form after settlement and plate and frame pressure filtration, the water content and oil content are more than 90%, and the cost of solid waste treatment is relatively large.

[0041] After adding 200 PPM of the demulsifier of the application, the petroleum coke and salt are effectively settled, and the moisture content of the filter cake after pressure filtration is as low as 60%, thereby reducing the solid waste treatment cost of the enterprise by more than 35%.

[0042] Embodiment 3: The embodiment discloses a calcined coke sewage demulsifier prepared from the following components:

[0043] A calcined coke sewage demulsifier, characterized in that the raw materials include the following components by weight percentage: 20% of a modified amide demulsifying main agent, 15% of a cationic organic matter, 3% of a heavy metal capturing agent, 3% of a defoaming agent, and the balance of water; and the sewage demulsifier product is obtained after stirring for more than 40 minutes.

[0044] A certain aluminum can manufacturing plant has a large amount of aluminum powder, a small amount of paint powder, and trace amounts of machine oil entering during the casting process in the end sewage, which is difficult to separate in water and has a turbidity of 1500-2000 NTU.

[0045] After adding 200 PPM of the demulsifier of the application, the powder and oil are effectively separated; the oil separation tank is cleaned and scraped by a scraper, and the turbidity of the water layer is less than 20 NTU.

[0046] As can be seen from the above embodiments, the calcined coke sewage demulsifier of the application performs well in the application of different industrial sewage, can effectively solve the sewage problem, reduce the treatment cost, and can adapt to different sewage characteristics, and has a broad application prospect in actual industrial sewage treatment.

[0047] The steel plant sewage has the problems of surface floating oil and high iron ion content (200-500 mg / L), and the traditional sedimentation flocculant is difficult to treat, so that the iron ions cannot be settled, the floating oil accumulates, the sewage cannot enter the biochemical system, and the drainage requirement cannot be met, affecting the normal operation of the enterprise. After adding 300 PPM of the demulsifier of the application in embodiment 1, the surface floating oil is eliminated, the iron ion content is reduced by 90%, the sewage can smoothly enter the subsequent treatment process and meet the discharge standard, and the treatment problem of the steel plant sewage is effectively solved.

[0048] Sponge titanium production plant sewage application effect: the sponge titanium production plant flushing impeller sewage contains petroleum coke, and the salt content is as high as 52%. After settling, the plate and frame pressure filtration is difficult to form, and the moisture and oil content is more than 90%, and the solid waste treatment cost is high. After adding 200 PPM of the demulsifier of the application in embodiment 2, the petroleum coke and salt are effectively settled, the moisture content of the filter cake after pressure filtration is reduced to 60%, the solid waste treatment cost of the enterprise is reduced by more than 35%, the treatment effect of the sewage is significantly improved, and the cost of the enterprise is reduced.

[0049] The application effect of the wastewater of the aluminum can manufacturing plant: the wastewater of the aluminum can manufacturing plant contains a large amount of aluminum powder, a small amount of paint powder and a trace amount of machine oil, which is difficult to separate in water, and the turbidity reaches 1500-2000 NTU. After adding 200 PPM of the demulsifier of the application in Example 3, the powder and oil are effectively separated, the water layer turbidity is reduced to below 20 NTU after the oil separation tank is cleaned by the scraper, the efficient separation of solid-liquid and oil-water in the wastewater is realized, and the water quality is improved.

[0050] The above embodiments are only used to illustrate the technical solutions of the present application, but not to limit them; although the present application has been described in detail with reference to the above embodiments, those skilled in the art should understand that they can still modify the technical solutions recorded in the above embodiments, or make equivalent replacement for part or all of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the scope of the technical solutions of the embodiments of the present application; any alternative improvement or change made by those skilled in the art to the embodiments of the present application falls within the protection scope of the present application.

[0051] The parts not described in detail in the present application are the known technology of those skilled in the art.

Claims

1. A wastewater demulsifier for calcined coke, characterized by, Comprise the following weight percentage of components: 10%-30% modified amide demulsifying main agent, 10%-20% cationic organic matter, 1%-3% heavy metal capture agent, 1%-3% defoaming agent and the balance water; The synthesis components of the modified amide demulsifying main agent include starter, catalyst and chain extender; the starter is cellulose and the chain extender is urea; The preparation method of the modified amide demulsifying main agent is: Step 1) taking cellulose as raw material, reacting with ethylene oxide under alkaline condition to obtain a first reaction intermediate; Step 2) adding urea solution dropwise to the substance obtained in step 1) to obtain an amine group terminated macromolecular substance, the reaction temperature is 90-120 DEG C, the reaction time is 2-4 hours, and the catalyst used in the reaction is an organic or inorganic catalyst; The organic or inorganic catalyst in step 2) is sodium methoxide, sodium cyanide or copper sulfate catalyst; The cationic organic matter is one or both of tetramethylammonium chloride and polyamine; The heavy metal capture agent is one or both of TMT and sulfide.

2. The calcined coke wastewater demulsifier according to claim 1, characterized in that: The defoaming agent is one or both of high carbon alcohol defoaming agent and polyether defoaming agent.

3. A method for preparing a calcined coke wastewater demulsifier, characterized by: The calcined coke wastewater demulsifier is the calcined coke wastewater demulsifier described in claim 1, and the preparation method thereof comprises the following steps: S1, preparing a modified amide demulsifying main agent: 1) taking cellulose as raw material, reacting with ethylene oxide under alkaline condition to obtain a first reaction intermediate; 2) adding urea solution dropwise to the substance obtained in step 1) to obtain an amide group terminated macromolecular substance, the reaction temperature is 90-120 DEG C, the reaction time is 2-4 hours, and the catalyst used in the reaction is an organic or inorganic catalyst; S2, weighing a certain mass of deionized water or pure water into a mixing kettle, then adding 10%-30% modified amide demulsifying main agent, 10%-20% cationic organic matter, 1%-3% heavy metal capture agent and 1%-3% defoaming agent, stirring for 30-40 min until the system is uniform to obtain a mixed solution.