阅读说明：本技术 一种磁性无机黏土-石墨烯复合破乳材料的制备及其应用 (Preparation and application of magnetic inorganic clay-graphene composite demulsification material ) 是由 王金清 徐海燕 杨生荣 于 2019-09-24 设计创作，主要内容包括：本发明涉及一种磁性无机黏土-石墨烯复合破乳材料的制备,包括以下步骤：⑴将氧化石墨烯分散在聚乙烯亚胺水溶液中,静置后搅拌、抽滤、洗涤、冷冻干燥,即得氧化石墨烯复合物；⑵将六水合氯化铁分散在乙二醇中,然后依次加入醋酸钠和聚乙二醇、硅烷偶联剂修饰的无机黏土搅拌,在反应釜中反应后,经清洗、干燥,即得四氧化三铁-无机黏土复合物；⑶将氧化石墨烯复合物分散在去离子水中,得到10~100mg/L的溶液；⑷在溶液中加入四氧化三铁-无机黏土复合物,经搅拌、洗涤、干燥即得。本发明还公开了该材料对水包油型原油乳状液的分离应用。本发明方法简单、成本低廉,所得材料可同时实现对不同pH值水包油型原油乳状液的高效分离和对破乳材料的回收利用。(The invention relates to a preparation method of a magnetic inorganic clay-graphene composite demulsification material, which comprises the following steps of dispersing graphene oxide in a polyethyleneimine water solution, standing, stirring, filtering, washing and freeze-drying to obtain a graphene oxide compound, dispersing ferric chloride hexahydrate in ethylene glycol, sequentially adding sodium acetate, polyethylene glycol and inorganic clay modified by a silane coupling agent, stirring, reacting in a reaction kettle, washing and drying to obtain a ferroferric oxide-inorganic clay compound, dispersing the graphene oxide compound in deionized water to obtain a 10 ~ 100mg/L solution, adding the ferroferric oxide-inorganic clay compound into the solution, stirring, washing and drying to obtain the oil emulsion demulsification emulsion.)

1. The preparation method of the magnetic inorganic clay-graphene composite demulsification material comprises the following steps:

dispersing graphene oxide in a polyethyleneimine aqueous solution with the concentration of 0.01 ~ 1.0.0 wt%, enabling the concentration of the graphene oxide in the polyethyleneimine aqueous solution to be 0.01 ~ 0.5.5 wt%, standing for 1 ~ 5h, stirring at 60 ~ 120 ℃ for 3 ~ 8h, and performing suction filtration after the reaction is finished to obtain a product A, wherein the product A is sequentially subjected to multiple washing and freeze drying of absolute ethyl alcohol and deionized water to obtain a product graphene oxide compound;

dispersing ferric chloride hexahydrate in 15 ~ 50mL of glycol to enable Fe in the mixed solution³⁺Sequentially adding 0.1 ~.5 mol of sodium acetate and 0.5 ~.5 g of polyethylene glycol into 1L of mixed solution, stirring for 30 ~ min, dispersing 0.05 ~.5 g of inorganic clay modified by a silane coupling agent into the mixed solution, fully stirring, transferring the mixed solution into a reaction kettle, reacting at 150 ~ ℃ for 20 ~ h, cooling to room temperature to obtain a product B, recovering the product B by using a magnet, sequentially washing with deionized water and absolute ethyl alcohol for multiple times, and drying in vacuum to obtain the ferroferric oxide-inorganic clay compound;

dispersing the graphene oxide compound in deionized water to obtain a solution with the concentration of 10 ~ 100 mg/L;

fourthly, 0.01 ~ 5.0.0 g of the ferroferric oxide-inorganic clay compound is added into the solution obtained in the step three in the step 1L, mechanical stirring is carried out for 3 ~ 8 hours at the temperature of 60 ~ 120 ℃, a product C is obtained, and the product C is recovered by a magnet, fully washed by deionized water and absolute ethyl alcohol in sequence and dried, and the magnetic inorganic clay-graphene compound is obtained.

2. The preparation method of the magnetic inorganic clay-graphene composite demulsification material as claimed in claim 1, wherein the freeze drying conditions in the step are that the temperature is-50 ~ -10 ℃ and the time is 12 ~ 48 h.

3. The preparation method of the magnetic inorganic clay-graphene composite demulsification material as claimed in claim 1, wherein the preparation method comprises the following steps: the inorganic clay modified by the silane coupling agent is diatomite.

4. The preparation method of the magnetic inorganic clay-graphene composite demulsification material as claimed in claim 1, wherein the filling rate of the reaction kettle in the step is 50 ~ 80%.

5. The preparation method of the magnetic inorganic clay-graphene composite demulsification material as claimed in claim 1, wherein the vacuum drying condition in the step is that the temperature is 50 ~ 80 ℃ and the time is 24 ~ 48 h.

6. The preparation method of the magnetic inorganic clay-graphene composite demulsification material as claimed in claim 1, wherein the drying condition in the step four is that the temperature is 60 ~ 80 ℃ and the time is 12 ~ 36 h.

7. The application of the magnetic inorganic clay-graphene composite demulsification material prepared according to the method in the separation of the oil-in-water crude oil emulsion is characterized in that the magnetic inorganic clay-graphene composite demulsification material is dispersed in deionized water to obtain suspension with the concentration of 0.1 ~ 10.0.0 mg/mL, then the suspension is used for performing demulsification performance test on the oil-in-water crude oil emulsion at 25 ℃ according to a bottle test method, and after the demulsification performance test is finished, a magnet is used for recycling the composite demulsification material.

Technical Field

The invention relates to the technical field of inorganic materials, in particular to a preparation method and application of a magnetic inorganic clay-graphene composite demulsification material.

Background

Currently, the oil recovery and processing, textile industry, machining, solid fuel thermal processing, etc. (s. Bratskaya, v. Avramenko, s. Schwarz,Colloid Surface A2006, 275, 168-176) will produce a large amount of oil-water emulsion, with the majority of the emulsions produced during oil recovery and processing. Such emulsionsThe direct discharge of the oil causes serious environmental pollution, so that demulsification treatment must be carried out before the discharge.

It was found that graphene oxide (j. Liu, x. Li, w. Jia,Energ. Fuel.2015,29 (7): 4644-4653) and carbon nanotubes (J. Liu, X. Li, W. Jia,J. Disper. Sci. Technol.2015, 37(9): 1294-1302) can achieve efficient emulsion breaking under low dosage conditions, but the wide application thereof is limited due to the complicated preparation process. Therefore, the development of the demulsifier which is green, environment-friendly and low in price is very important.

China has abundant clay resources, and common inorganic clay comprises attapulgite, montmorillonite, diatomite, expanded perlite and the like. The material has the advantages of strong adsorption capacity, no corrosiveness, low cost and toxicity and the like (S.O. Esra Karaca, Okan Akcam,J. Appl. Polym.Sci.2016, 133, 431281-,J. Hazard. Mater., 2010, 177, 950-955). Previous studies found magnetic expanded perlite (EP @ APTES-Fe)₃O₄) The composite material is only pH-dependent at a concentration of 500mg/L<The oil-in-water emulsion of 7.0 has a good demulsifying effect (h. Xu, w. Jia, s. Ren,Chem. Eng. J., 2018, 337, 10-18). The prepared magnetic diatomite (M-DM) composite material can realize demulsification of oil-in-water emulsions with different pH values at the concentration of 450 mg/L (application number: 201910172144.8). However, M-DM is used in a large amount in the demulsification process, so that the wide application of the M-DM is limited.

Therefore, the existing modified inorganic clay material has the defects of large demulsifying agent amount or incapability of realizing high-efficiency separation of oil-in-water type emulsions with different pH values in the separation aspect of the oil-in-water type crude oil emulsion.

Disclosure of Invention

The invention aims to solve the technical problem of providing a preparation method of a magnetic inorganic clay-graphene composite demulsification material with simple method and low cost.

The invention also provides an application of the magnetic inorganic clay-graphene composite demulsification material.

In order to solve the problems, the preparation method of the magnetic inorganic clay-graphene composite demulsification material comprises the following steps:

dispersing graphene oxide in a polyethyleneimine aqueous solution with the concentration of 0.01 ~ 1.0.0 wt%, enabling the concentration of the graphene oxide in the polyethyleneimine aqueous solution to be 0.01 ~ 0.5.5 wt%, standing for 1 ~ 5h, stirring at 60 ~ 120 ℃ for 3 ~ 8h, and performing suction filtration after the reaction is finished to obtain a product A, wherein the product A is sequentially subjected to multiple washing and freeze drying of absolute ethyl alcohol and deionized water to obtain a product graphene oxide compound;

dispersing ferric chloride hexahydrate in 15 ~ 50mL of glycol to enable Fe in the mixed solution³⁺Sequentially adding 0.1 ~.5 mol of sodium acetate and 0.5 ~.5 g of polyethylene glycol into 1L of mixed solution, stirring for 30 ~ min, dispersing 0.05 ~.5 g of inorganic clay modified by a silane coupling agent into the mixed solution, fully stirring, transferring the mixed solution into a reaction kettle, reacting at 150 ~ ℃ for 20 ~ h, cooling to room temperature to obtain a product B, recovering the product B by using a magnet, sequentially washing with deionized water and absolute ethyl alcohol for multiple times, and drying in vacuum to obtain the ferroferric oxide-inorganic clay compound;

dispersing the graphene oxide compound in deionized water to obtain a solution with the concentration of 10 ~ 100 mg/L;

fourthly, 0.01 ~ 5.0.0 g of the ferroferric oxide-inorganic clay compound is added into the solution obtained in the step three in the step 1L, mechanical stirring is carried out for 3 ~ 8 hours at the temperature of 60 ~ 120 ℃, a product C is obtained, and the product C is recovered by a magnet, fully washed by deionized water and absolute ethyl alcohol in sequence and dried, and the magnetic inorganic clay-graphene compound is obtained.

The conditions of freeze drying in the first step are that the temperature is-50 ~ -10 ℃ and the time is 12 ~ 48 h.

The inorganic clay modified by the silane coupling agent is diatomite.

The filling rate of the reaction kettle in the step II is 50 ~ 80%.

The vacuum drying condition in the step II is that the temperature is 50 ~ 80 ℃ and the time is 24 ~ 48 h.

The drying condition in the step four is that the temperature is 60 ~ 80 ℃ and the time is 12 ~ 36 h.

The separation application of the magnetic inorganic clay-graphene composite demulsification material in the oil-in-water type crude oil emulsion is characterized in that the magnetic inorganic clay-graphene composite demulsification material is dispersed in deionized water to obtain suspension with the concentration of 0.1 ~ 10.0.0 mg/mL, then the suspension is adopted to carry out demulsification performance test on the oil-in-water type crude oil emulsion at 25 ℃ according to a bottle test method, and after the test is finished, a magnet is utilized to recycle the composite demulsification material.

Compared with the prior art, the invention has the following advantages:

1. according to the invention, graphene oxide is successfully compounded on the surface of inorganic clay by a simple surface modification means, so that the inorganic clay-graphene composite demulsification material with recyclable magnetism is prepared.

2. The invention realizes the high-efficiency separation of oil-in-water crude oil emulsion with different pH values by using inorganic materials under the condition of low dosage, and solves the technical problems that the existing demulsifier can not simultaneously meet the requirements of cheap and easily obtained raw materials, high-efficiency separation of oil-in-water crude oil emulsion under low dosage, and reduction of recovery cost and environmental pollution by recycling of the demulsifier.

3. The inorganic clay in the composite demulsifying material has wide sources, is cheap and is easy to obtain.

4. The composite demulsifying material obtained by the invention has excellent demulsifying performance under different pH (acidic, neutral and alkaline) conditions. Compared with inorganic clay, the dosage of the compound is obviously reduced when demulsification is carried out.

With the increase of the dosage of the demulsifier, the oil content in the water-in-water type emulsion is gradually reduced, and the demulsification efficiency is gradually increased. When the dosage of the composite demulsifying material is increased to 350mg/L, the demulsification efficiency of the oil-in-water crude oil emulsion with the pH =4.0 can reach 92.2% at most (see figure 1); the demulsification efficiency of the oil-in-water crude oil emulsion with pH =6.0 was 96.8% (see fig. 2); the demulsification efficiency of the oil-in-water crude oil emulsion with pH =8.0 was 85.8% (see fig. 3).

5. The composite demulsifying material has the characteristic of quick separation and recovery in a magnetic field, and the utilization rate of the composite material is improved.

6. The composite demulsification material disclosed by the invention can still achieve the demulsification efficiency of over 90% after 5 times of cyclic utilization (see fig. 4), so that the multiple cyclic utilization of the demulsification material is realized, the circulating stability is higher, and the demulsification cost is reduced.

Drawings

The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.

Fig. 1 is a diagram for analyzing the demulsification effect of the composite demulsification material on an oil-in-water crude oil emulsion with the pH = 4.0.

Fig. 2 is a diagram for analyzing the demulsification effect of the composite demulsification material on an oil-in-water crude oil emulsion with the pH = 6.0.

Fig. 3 is a diagram for analyzing the demulsification effect of the composite demulsification material on an oil-in-water crude oil emulsion with the pH = 8.0.

FIG. 4 is a graph of the circulating demulsification efficiency of the composite demulsification material under the condition of pH = 6.0.

Detailed Description