CN114940887A - Offshore oil spill oil condensing agent, and preparation method and application thereof - Google Patents

Abstract

The invention discloses a condensing agent for marine oil spills, a preparation method and application thereof, and belongs to the technical field of environmental protection. The marine oil spill condensing agent of the present invention is composed of xylenol and aluminum isooctanoate in a mass ratio of 1:1.2 to 1:2, and has good oil condensing effect. After being added to oil products, under the action of external force , the gel can be formed in about 60 seconds, the speed of condensing oil is fast, and the formed gel has good stability, no stratification, and poor fluidity, which is easy to salvage. At the same time, the present invention also innovatively provides a method for fast coagulation, which is to first add aluminum isooctanoate into the oil, and then add xylenol according to the mass ratio to coagulate the oil. Under this method, the gel will immediately It can not only prevent the oil film from spreading and control the oil spill in a small range, but also shorten the oil salvage time and save time and cost.

Description

A kind of marine oil spilled condensing agent, its preparation method and application

technical field

The invention belongs to the technical field of environmental protection, and particularly relates to a condensing agent for marine oil spills, a preparation method and application thereof.

Background technique

Marine oil pollution not only seriously affects the life of marine animals and plants, destroys the marine ecological balance, but also damages the atmospheric environment and affects human health. Offshore oil transportation, as the main means of trade, satisfies the large demand and use of petroleum products in human daily life, and also leads to the occurrence of offshore oil spill accidents. According to statistics, 2 to 4 large-scale marine oil spill accidents occur every year in the world. The largest 182 crude oil spill accidents since 1965 have leaked nearly 9 million tons of crude oil, causing serious ecological, economic and social losses.

Oil gelling agents are generally dry particulate hydrophobic polymers that react with oil slicks to form tightly bound solid oil clumps that float on water. The condensate can easily absorb the oil spilled on the water, and the oil slick treated by the condensate can be tightly aggregated to form a substance that can maintain a certain shape and is not easy to separate. After the condensate is evenly spread on the sea surface with oil spills, the condensate and the oil film are slowly combined under the action of the ocean waves, and finally form a mixed solid in the form of a block or sheet. The solidified oil slick can be used for oil recovery The net is easily recycled, thereby reducing residues and contamination from subsequent recycling. However, in the current oil spill accident handling, the amount of condensing agent used is generally large. To achieve a better condensing effect, the agent-oil ratio needs to reach 16-200%, which will undoubtedly increase the condensing agent. Input and spill disposal costs.

Meng Wei and other scholars synthesized and tested the properties of different fatty acid salt gelling agents, and studied the influence of structural factors and external environmental factors on the gelling properties of the gelling agent. After screening and comparison, it was determined that aluminum isooctanoate was qualified. condensate. However, the fatty acid salt gelling agent is limited by its own structure, and the number of lipophilic groups and hydroxyl groups is small, which limits its gelling ability. Based on factors such as cost saving and reducing the difficulty of synthesis, the scholar does not change the aluminum isooctanoate. On the basis of the structure of the coagulant, the aluminum isooctanoate coagulant can be improved by adding benzoic acid to form a compound coagulant to improve the coagulant ability of the coagulant (Meng Wei, Synthesis and Performance Research, East China University of Science and Technology Dissertation).

However, in practice, we found that the aluminum isooctanoate gelling agent compounded with benzoic acid still has some defects in terms of the speed of condensation and the effect of condensation. For example, after condensation, with the passage of time, the formation of The gel will be delaminated, and the aluminum isooctanoate will settle, resulting in the elimination of the gel phenomenon, which will not be conducive to the salvage of oil spills on the sea surface. At the same time, aluminum isooctanoate forms hydrogen bonds during the gelation process of condensed oil, and hydroxyl groups play an important role. The formed block gel has a certain spatial network structure and viscoelasticity. However, when the external stress is too large , the bulk gel is prone to dissociation, resulting in the fragmentation of the gel, which is not conducive to the salvage of the gel. Therefore, it is of great significance to develop a gelatinizer with fast oil condensation speed and stable gel formation.

SUMMARY OF THE INVENTION

In order to overcome the technical problems existing in the prior art, the present invention provides a condensing agent for marine oil spillage, which is composed of xylenol and aluminum isooctanoate in a mass ratio of 1:1.2-2.

The preparation method of above-mentioned marine oil spilled gelling agent is as follows: take aluminum iso-octoate and xylenol by mass ratio, pour xylenol into aluminum isooctanoate, stir and mix to obtain isooctanoic acid compounded by xylenol The aluminum condensate is the marine oil condensate described in the present invention.

The above-mentioned marine oil-spill gelling agent has a good oil-coagulating effect. After being added to the oil product, under the action of external force (such as stirring, wave impact, etc.), it will form a gel in about 60 seconds. The gel has good stability, does not delaminate, and has poor fluidity, which is easy to salvage. Based on the above technical effects, the present invention provides the application of the above-mentioned marine oil condensate agent in the treatment of marine oil condensate.

In the above application, the mass ratio of the condensate for marine oil spills to the oil product is 1-1.5:10.

During the research process, we found that in the process of condensing oil, if aluminum isooctanoate is added to the oil first, and then xylenol is added, the gel will form immediately, and there is basically no buffer time. For oil spill gelling agents, the formation speed of gel is further accelerated, and the effect is remarkable.

Based on the above content, the present invention also provides a method for rapid coagulation of oil, the steps of which are: firstly adding aluminum isooctanoate to the oil product, and then adding xylenol according to the mass ratio, so as to achieve the purpose of rapid coagulation of oil.

In the above-mentioned quick-setting oil method, the mass ratio of xylenol, aluminum isooctanoate and oil product is 1:1.2～2:20. Preferably, the mass ratio of xylenol, aluminum isooctanoate and oil is 1:1.2:20.

On the basis of the above technical solutions, the above-mentioned rapid oil condensing method can be applied to the oil condensing treatment of marine oil spill accidents, so as to increase the oil condensing speed, prevent the oil film from spreading, control the oil spill in a small range, and save time and cost.

The beneficial effects of the present invention are:

The density of xylenol is close to that of water, slightly soluble in water, soluble in most organic solvents, easier to enter the oil phase, attached to the water surface, without causing water pollution. It has the characteristics of fast oil condensation speed and good oil condensation effect, and the formed gel has good stability, no stratification, and poor fluidity, so it is easy to salvage. In addition, the present invention also innovatively provides a method for rapid condensing oil, which is to first add aluminum isooctanoate into the oil product, and then add xylenol according to the mass ratio for condensing oil. Under this method, the gel will immediately It can not only prevent the oil film from spreading and control the oil spill in a small range, but also shorten the oil salvage time and save time and cost.

Description of drawings

Figure 1 shows the effect of the gelling agent, reflecting the initial formation state of the oil gel; the left picture is xylenol compounded with aluminum isooctanoate gelling agent, and the right picture is benzoic acid compounded with aluminum isooctanoate gelling agent oil;

Figure 2 shows the effect of condensing oil of the oil gel, reflecting the fluidity of the oil gel after horizontal placement; the left picture is xylenol compounded with aluminum isooctanoate oil condensing agent, and the right picture is benzoic acid compounded with isooctanoic acid Aluminum condensate;

Figure 3 shows the performance of the oil gel after being placed for one day; the picture on the left is xylenol compounded with aluminum isooctanoate gel, and the picture on the right is benzoic acid compounded with aluminum isooctanoate gel;

Figure 4 shows the effect of condensation of aluminum isooctanoate and xylenol in different addition sequences, reflecting the initial formation state of the oil gel; the left picture is the first addition of aluminum isooctanoate, and the right picture is the first addition of xylenol ;

Figure 5 shows the effect of the oil condensation of aluminum isooctanoate and xylenol in different addition sequences, reflecting the fluidity of the oil gel after horizontal placement; the left picture is the first adding aluminum isooctanoate, and the right picture is the first adding two cresol;

Figure 6 shows the performance of the oil gel after being placed for one day; among them, the left picture is the first addition of aluminum isooctanoate, and the right picture is the first addition of xylenol;

Figure 7 is a diagram showing the effect of condensed oil under different additive conditions, wherein the left picture is a schematic diagram of a gel formed by using xylenol as an additive, and the right picture is a schematic diagram of the gel formed by using benzoic acid as an additive;

Figure 8 is the performance diagram of the oil gel after being placed for one day under different additive conditions, which reflects the formation state of the oil gel. The left picture is a schematic diagram of the gel formed by xylenol as an additive, and the right picture is benzoic acid. Schematic diagram of the gel formed by the additive;

Figure 9 is the performance diagram of the oil gel after being placed for one day under the condition of different additives, reflecting the fluidity of the oil gel after horizontal placement. The left picture is a schematic diagram of the gel formed by xylenol as an additive, and the right picture is Schematic diagram of the gel formed with benzoic acid as additive;

Fig. 10 is the AFM topography of oleogel;

Figure 11 is the infrared spectrum of the oil gel.

Detailed ways

The aluminum isooctanoate adopted in the present invention is a white powder, and its structural formula is as follows:

The xylenol used in the present invention is a mixture of six isomers, and its structural formula is as follows:

The petroleum ether used in the present invention has a boiling range of 90-120 DEG C, and is mainly a mixture of _C6 -C8 _alkanes .

Terms used in the present invention generally have the meanings commonly understood by those of ordinary skill in the art unless otherwise specified. The present invention will be described in further detail below with reference to specific embodiments and data. The following examples are only intended to illustrate the present invention and are not intended to limit the scope of the present invention in any way.

Example 1 Marine oil spill condensate

Preparation of xylenol compound aluminum isooctanoate gelling agent:

Option 1: Weigh 12 g of aluminum isooctanoate and 10 g of xylenol, pour the xylenol into the aluminum isooctanoate, stir to mix the two, and obtain an aluminum isooctanoate coagulant compounded by xylenol.

Scheme 2: Weigh 15 g of aluminum isooctanoate and 12.5 g of xylenol, pour the xylenol into the aluminum isooctanoate, stir, and mix the two to obtain an aluminum isooctanoate coagulant compounded by xylenol.

Example 2 Test of gelling effect of gelling agent

1. Set the comparison

Aluminum isooctanoate gel oil formulated with benzoic acid. Its preparation method is as follows:

Weigh 12 g of aluminum isooctanoate and 10 g of benzoic acid, pour the benzoic acid into the aluminum isooctanoate, stir, and mix the two to obtain the aluminum isooctanoate coagulant compounded with benzoic acid.

2. Condensation effect test

Weigh two parts of petroleum ether with a mass of 200g, respectively pour the aluminum isooctanoate gelatinizer compounded by benzoic acid and the xylenol compounded by scheme 1 into the petroleum ether, and continuously stir, Observe the gel formation time. The formed gel was then left for one day to observe gel stability.

The test results are shown in Table 1:

Table 1

Example 3 Exploration of quick-setting oil method

1. The order of addition of aluminum isooctanoate and xylenol

Two parts of petroleum ether with a mass of 200g were weighed, and the following operations were carried out respectively: (1) firstly add 12g of aluminum isooctanoate, stir evenly, then add 10g of xylenol, keep stirring, and observe the gel formation time; (2) first Add 10 g of xylenol, stir evenly, and then add 12 g of aluminum isooctanoate, keep stirring, and observe the gel formation time. Finally, the formed gel was left for one day to observe the gel stability.

The test results are shown in Table 2:

Table 2

It can be seen from Table 2 that in the process of condensing oil, the strategy of adding aluminum isooctanoate first and then adding xylenol can quickly condense the oil, effectively prevent the oil film from spreading, and the formed gel has good stability and flow. It has poor performance and provides favorable conditions for subsequent salvage.

2. Comparative analysis of xylenol and benzoic acid

Two parts of petroleum ether with a mass of 200 g were weighed, 12 g of aluminum isooctanoate were added, and stirred evenly, then 10 g of xylenol and 10 g of benzoic acid were added respectively, and the gel formation time was observed with constant stirring. The formed gel was then left for one day to observe gel stability.

The test results are shown in Table 3:

table 3

It can be seen from Table 3 that under the strategy of "adding aluminum isooctanoate first, and then adding additives", xylenol exhibits better oil condensation properties than benzoic acid. The reason is that, as mentioned by Meng Wei and other scholars, the density of benzoic acid is higher than that of the gelling agent (aluminum isooctanoate), and it will sink to the bottom of the sea when it is in the oil-water system alone. The effect of benzoic acid can only be exerted by fully mixing aluminum isooctanoate and benzoic acid in advance to prepare a compound gelling agent. The density of xylenol is close to that of water, slightly soluble in water, and soluble in most organic solvents. It is easier to enter the oil phase, thereby interacting with aluminum isooctanoate and promoting the rapid formation of gel. From this point of view, benzoic acid is not suitable for the coagulation strategy of "adding aluminum isooctanoate first, and then adding additives", but xylenol can be prepared as a compound coagulant or directly in the coagulation process. It has a wider range of applications than benzoic acid.

Example 4 Characterization of physical and chemical properties of oil gel

Weigh 200g of petroleum ether into a beaker, slowly add 12g of aluminum isooctanoate while stirring, and after complete addition, stir for 3 minutes to make it evenly mixed; then slowly add 10g of xylenol to the above mixed solution while stirring, and fully stir for 5min , resulting in a brown gel.

Taking the above brown gel as a sample, the characterization of physical and chemical properties is carried out. The specific operations are as follows:

First, use double-sided tape to expose a new mica sheet, draw 5-10 μL of the sample solution and drop it on the mica sheet, absorb it at room temperature for 5 min, blow dry with N ₂ , and then place it on the stage for detection. In this experiment, the TESP model probe is used, the mode is Tapping Mode, the scanning rate is 1.0~1.5Hz, the scanning angle is 0°, the operating frequency is 288kHz, and the resolution is 512×512. Then use the analysis software that comes with AFM for processing.

The experimental samples were measured by ATR-FTIR on a VERTEX 70FTIR series (Bruker) at room temperature, and the scanning range of the data was 400-4000 cm ^-1 .

The test results are as follows:

It can be seen from Figure 10 that the morphology of the gel is a network, which indicates that the interaction of aluminum isooctanoate to form hydrogen bonds to make it cross-linked into a network, thereby encapsulating the oil. It can be seen from Figure 11 that the peak at 3736cm ^-1 is the absorption peak of aluminum isooctanoate-OH, which is a smaller and narrower peak; the hydrogen bond peak at 3621cm ^-1 has shifted to the lower band, and the new peak at 3381cm ^-1 appears wider, indicating that the gelling agent formed more hydrogen bonds over time during the gelation process.

According to the above characterization results of physical and chemical properties, the principle of condensed oil is inferred, as shown in the following structure: the dehydration of the hydroxyl group of isooctanoic acid between aluminum isooctanoate interacts to form a network, and the petroleum ether is wrapped in it, so that the petroleum ether is transformed from a liquid state to a network. It transforms into a gel, and xylenol accelerates the interaction between aluminum isooctanoate and promotes the rapid formation of gel.

The above are only preferred embodiments of the present invention, and are not intended to limit the present invention in other forms. Any person skilled in the art may use the technical content disclosed above to make changes or modifications to equivalent changes. Example. However, any simple modifications, equivalent changes and modifications made to the above embodiments according to the technical essence of the present invention without departing from the content of the technical solutions of the present invention still belong to the protection scope of the technical solutions of the present invention.

Claims (8)

1. The offshore oil spill oil condensing agent is characterized by comprising xylenol and aluminum isooctanoate according to the mass ratio of 1: 1.2-2.

2. The preparation method of the offshore oil spill condensate of claim 1, which is characterized by comprising the following steps: weighing aluminum isooctanoate and xylenol according to the mass ratio, pouring the xylenol into the aluminum isooctanoate, and uniformly stirring to obtain the xylenol compounded aluminum isooctanoate oil condensate, namely the offshore oil spill oil condensate.

3. Use of a marine spill oil condensate as claimed in claim 1 in a marine spill oil condensate treatment.

4. The application of claim 3, wherein the mass ratio of the offshore oil spill condensate to the oil product is 1-1.5: 10.

5. The quick oil solidifying method is characterized by comprising the following steps: adding aluminum isooctanoate into oil product, and adding dimethyl phenol according to mass ratio to achieve the purpose of quick oil condensation.

6. The fast oil-setting method according to claim 5, wherein the mass ratio of the xylenol to the aluminum isooctanoate to the oil is 1: 1.2-2: 20.

7. The fast oil-setting method of claim 6, wherein the mass ratio of the xylenol, the aluminum isooctanoate and the oil product is 1:1.2: 20.

8. Use of the rapid oil condensation method according to any one of claims 5 to 7 in offshore oil spill condensation treatment.

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