Preparation method of novel lithium ion sieve for extracting lithium from oil and gas field produced water

Abstract

The invention relates to the technical field of lithium resource recovery, and particularly discloses a preparation method of a novel lithium ion sieve for extracting lithium from oil and gas field produced water. The preparation method of the novel lithium ion sieve comprises the following steps: step 1, mixing and oxidizing a manganese source and a lithium source according to a certain manganese-lithium ratio, drying, and calcining in a muffle furnace for the first time to obtain powder; and 2, uniformly mixing the water-soluble lanthanum salt in the step 1 according to a ratio, co-precipitating, calcining for the second time to obtain a novel lithium ion sieve precursor, and removing lithium from hydrochloric acid to obtain the novel lithium ion sieve for extracting lithium from the oil and gas field produced water. The stability is prominent by means of rare earth oxygen metal, the stability of lithium extraction of the novel lithium ion sieve in oil and gas field produced water is guaranteed, the loss rate of manganese is reduced to 1%, and the cycle adsorption frequency is increased.

Description

Technical Field

[0001] The invention belongs to the technical field of lithium resource recovery, and in particular relates to a method for preparing a novel lithium ion sieve for extracting lithium from produced water in oil and gas fields. Background Art

[0002] Lithium is known as the "energy metal" and "important element to drive the world forward" in the 21st century. It is one of the 36 strategic minerals established by the country. Since lithium is widely used in high-performance greases, heat-resistant ceramics, energy storage, batteries and other fields, lithium supply has become a hot issue that needs to be solved at present. At present, lithium resources mainly include liquid lithium resources and solid lithium mines. Among them, oil and gas field produced water is the high-salt wastewater returned in the process of unconventional oil and gas production. It is a hidden large-scale liquid lithium source and contains a certain concentration of lithium resources. At present, the oil and gas field water produced in oil (gas) fields in the United States, Germany and Canada has good lithium resources, and some oil and gas field water in the United States and Canada are already in lithium extraction projects and have generated income. The research history of oilfield water in the Jianghan Basin in China has a long history. The content of the Shashi Formation and the Xingouzui Formation produced in the Jiangling Depression is considerable, 52-62 mg / L. Therefore, a low-cost, environmentally friendly and efficient lithium extraction technology is urgently needed to provide a new way for the resource utilization of wastewater.

[0003] At present, there are three methods for extracting lithium from liquid lithium sources: extraction, precipitation and adsorption. The precipitation method is not applicable due to the insolubility of lithium carbonate. The extraction method is easily affected by organic matter in oil and gas field produced water, and the extractant is expensive, so its industrialization is hindered. Lithium ion sieves have large adsorption capacity and good lithium selectivity, and have the potential for industrialization. In order to recover lithium, aluminum salt adsorbents, antimony acid adsorbents, and titanium oxide adsorbents have been developed. The common disadvantage of these materials is that they are expensive and not suitable for large-scale lithium-containing wastewater such as oil and gas field produced water. Therefore, it is of great practical significance to find a lithium adsorption material that is simple to prepare, has a high lithium adsorption capacity, and can be recycled many times. Summary of the invention

[0004] In view of this, in order to solve at least one technical problem in the related art and other aspects, the present disclosure proposes a preparation method for a new lithium ion sieve for extracting lithium from produced water in oil and gas fields. The method comprises: firstly, obtaining a precursor powder through a first solid phase calcination; then mixing the above-mentioned precursor powder with a water-soluble lanthanum salt in proportion, and performing a second calcination for surface modification. The second calcination retains the precursor spinel configuration, and the precursor is fully soaked in an inorganic acid solution, filtered and dried to obtain a new lithium ion sieve.

[0005] By adopting the above technical solution, the present application uses the coprecipitation method to prepare the precursor, which is low in cost. At the same time, the ion sieve retains the advantage of high adsorption capacity of manganese-based ion sieve after desorption, and then the new lithium ion sieve precursor is synthesized by the second coprecipitation method, and the inorganic salt is soaked and dried to obtain the new lithium ion sieve. Compared with traditional ion sieve products, the synthesized new ion sieve has a higher lithium adsorption capacity, and the stable rare earth metal surface modification effectively improves the structural stability of the ion sieve. The manganese loss rate of the new lithium ion sieve during the lithium adsorption process is significantly reduced, thereby promoting the manufactured new lithium lithium ion sieve to have a higher lithium saturation adsorption capacity and adsorption efficiency.

[0006] The technical solution of the present invention is as follows:

[0007] The lithium source and manganese source are mixed in advance, dissolved in deionized water, the mixed solution is placed in a magnetic stirrer and stirred at room temperature, and hydrogen peroxide is slowly dripped in. This process is conducive to the full mixing and oxidation of the manganese source and the lithium source, and is more conducive to the co-precipitation reaction, thereby promoting the prepared lithium ion sieve to have a higher lithium saturation adsorption capacity and adsorption efficiency.

[0008] A novel method for preparing a lithium ion sieve for extracting lithium from produced water in oil and gas fields comprises the following steps:

[0009] S1: mixing a manganese source and a lithium source, stirring, and adding an oxidant to form a manganese-lithium mixed solution, filtering the mixed solution through precipitation to obtain a primary filter cake and a primary filtrate, washing with water for multiple times, and drying to form a solid mixture; performing a first calcination in a muffle furnace to synthesize an ion sieve precursor material having a spinel structure;

[0010] S2: The ion sieve precursor material obtained in S1 is uniformly mixed with a water-soluble lanthanum salt, and a precipitant is used and slowly injected into a reaction container. After the reaction is completed, the reactants are repeatedly precipitated, washed, and filtered, placed in a vacuum drying oven, and placed in a muffle furnace for a second calcination to obtain a novel lithium ion sieve precursor;

[0011] S3: S2 is calcined to obtain a novel lithium ion sieve precursor, which is then soaked in an inorganic acid solution, filtered and dried to obtain a novel lithium ion sieve.

[0012] Furthermore, the manganese source is manganese carbonate, manganese chloride or manganese sulfate; the lithium source is lithium hydroxide, lithium chloride or lithium carbonate; and the water-soluble lanthanum salt is lanthanum chloride or lanthanum nitrate.

[0013] Furthermore, the mass ratio of the manganese source to the lithium source is (1-1.5):1.

[0014] Further, in S1, the mixture is washed with water for multiple times until the pH value of the filtrate is between 7.2 and 8.

[0015] Furthermore, during the stirring in S1, hydrogen peroxide is used as an oxidant in an amount of 3-5% by volume of the manganese-lithium mixed solution, and is added slowly to prevent overflow;

[0016] During the stirring and mixing in S1, the stirring speed is 400-600 rpm, the temperature is 25-45° C., and the time is 1-4 h.

[0017] Furthermore, in S1, the first calcination is carried out in a muffle furnace, the calcination temperature is 450° C.-500° C., and the calcination time is 7-8 hours.

[0018] Furthermore, the novel lithium ion sieve is surface-modified by lanthanum oxide.

[0019] Furthermore, during the uniform mixing in S2, the precipitant is aqueous ammonia, and the amount used is 5-8% of the volume of the mixed solution.

[0020] Furthermore, the mixture of the water-soluble lanthanum salt and the ion sieve precursor material in step S1 is ball-milled until the particle size reaches micrometer level.

[0021] Furthermore, the mass ratio of the water-soluble lanthanum salt to the ion sieve precursor material in step S1 is (1.5-3):1.

[0022] Furthermore, in S2, a second calcination is carried out in a muffle furnace, the calcination temperature is set at 750° C.-900° C., and the calcination time is 8-15 hours.

[0023] Furthermore, the inorganic acid in S3 is hydrochloric acid, sulfuric acid or nitric acid; the concentration of the inorganic acid is 0.5-1M, and the mass ratio of the novel lithium ion sieve to the inorganic acid solution is 1:(60-100).

[0024] The technical solution of the present invention has the following advantages:

[0025] (1) By adopting the above technical solution and adjusting the amount of ammonia water used within a suitable range, the prepared lithium ion sieve can have a good pore structure and structural stability, and can maintain the lithium ion sieve with strong adsorption performance and recycling rate. By adding ammonia water, these metal ions can be precipitated, thereby forming a uniform metal hydroxide coating on the surface of the ion sieve.

[0026] (2) Relying on the outstanding stability of rare earth metal oxides, the stability of lithium extraction from oil and gas field produced water is guaranteed by the new lithium ion sieve. While ensuring that the lithium ion sieve has good adsorption selectivity and adsorption capacity, the manganese loss rate is reduced to 1%.

[0027] (3) By adopting the above technical solution, a certain concentration of inorganic salt can be desorbed, causing lithium to be deintercalated, forming a new type of lithium ion sieve with memory effect. At the same time, hydrochloric acid can dissolve and remove impurities, thereby improving the purity and crystallinity of the lithium ion sieve. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 The present invention is a flow chart of a method for preparing a novel lithium ion sieve for extracting lithium from produced water in oil and gas fields. Specific implementation plan

[0029] In the following examples, we describe the specific implementation of the present invention in detail to help understand the specific operation of the present invention. These examples do not constitute a limitation of the present invention, and any individual or entity, under the inspiration of the present invention, by combining the features of the present invention with the prior art, obtains any product identical or similar to the present invention, which belongs to the protection scope of the present invention.

[0030] For experimental steps or conditions not described in detail in the examples, standard experimental procedures or conditions in the literature of the relevant field can be referred to. The reagents or instruments used are all standard reagent products available on the market unless the manufacturer is specifically specified.

[0031] The present application is further described in detail below with reference to the embodiments.

[0032] Example 1

[0033] This embodiment provides a novel lithium ion sieve preparation method for extracting lithium from produced water in oil and gas fields, comprising the following specific steps:

[0034] (1) Preparation of lithium ion sieve precursor:

[0035] S1: Pre-mix 1g of manganese carbonate and 1g of lithium hydroxide uniformly, and ball-mill to micron level.

[0036] S2: Dissolve in deionized water, place the mixed solution in a magnetic stirrer and stir at a speed of 400 rpm, a temperature of 25°C, and a time of 1 hour. During the stirring process, slowly add 3 ml of a 30% hydrogen peroxide solution. S3: Filter and dry to obtain a mixed powder.

[0037] S4: calcining the powder in S3 at 450° C. for 7 h in an air atmosphere to obtain a lithium ion sieve precursor material.

[0038] (2) Surface modification:

[0039] S1: Mix 1 g of the lithium ion sieve precursor material synthesized in step (1), 1.5 g of lanthanum nitrate, and 5 ml of ammonia water for reaction, stir at 25°C, at a speed of 400 rpm, for 2 h to obtain a slurry, filter, wash, and dry to obtain a powder.

[0040] S2: The powder described in S1 is calcined at 750°C for 8 hours in an air atmosphere to obtain a novel lithium ion sieve precursor material. (3) Lithium removal:

[0041] The novel lithium ion sieve precursor material described in step (2) is soaked in a 0.5M hydrochloric acid solution to complete lithium deintercalation, filtered and dried to obtain a novel lithium ion sieve.

[0042] Example 2

[0043] This embodiment provides a novel lithium ion sieve preparation method for extracting lithium from produced water in oil and gas fields, comprising the following specific steps:

[0044] (1) Preparation of lithium ion sieve precursor:

[0045] S1: 1.1 g of manganese carbonate and 1 g of lithium hydroxide were uniformly mixed in advance and ball-milled to micron size.

[0046] S2: Dissolve in deionized water, place the mixed solution in a magnetic stirrer and stir at a speed of 500 rpm, a temperature of 30°C, and a time of 2 hours. During the stirring process, slowly add 4 ml of a 30% hydrogen peroxide solution. S3: Filter and dry to obtain a mixed powder.

[0047] S4: calcining the powder in S3 at 450° C. for 7 h in an air atmosphere to obtain a lithium ion sieve precursor material.

[0048] (2) Surface modification:

[0049] S1: Mix 1 g of the lithium ion sieve precursor material synthesized in step (1), 1.4 g of lanthanum nitrate, and 6 ml of ammonia water for reaction, stir at 25°C, at a speed of 400 rpm, for 2 h to obtain a slurry, and filter, wash, and dry to obtain a powder.

[0050] S2: The powder described in S1 is calcined at 850°C for 8 hours in an air atmosphere to obtain a novel lithium ion sieve precursor material. (3) Lithium removal:

[0051] The novel lithium ion sieve precursor material described in step (2) is soaked in a 0.6M hydrochloric acid solution to complete lithium deintercalation, filtered and dried to obtain a novel lithium ion sieve.

[0052] Example 3

[0053] This embodiment provides a novel lithium ion sieve preparation method for extracting lithium from produced water in oil and gas fields, comprising the following specific steps:

[0054] (1) Preparation of lithium ion sieve precursor:

[0055] S1: 1.2 g of manganese carbonate and 1 g of lithium hydroxide were uniformly mixed in advance and ball-milled to micron size.

[0056] S2: Dissolve in deionized water, place the mixed solution in a magnetic stirrer and stir at a speed of 550 rpm, a temperature of 35°C, and a time of 2 hours. During the stirring process, slowly add 4 ml of a 30% hydrogen peroxide solution. S3: Filter and dry to obtain a mixed powder.

[0057] S4: calcining the powder in S3 at 450° C. for 7 h in an air atmosphere to obtain a lithium ion sieve precursor material.

[0058] (2) Surface modification:

[0059] S1: Mix 1 g of the lithium ion sieve precursor material synthesized in step (1), 1.3 g of lanthanum nitrate, and 7 ml of ammonia water for reaction, stir at 25°C, at a speed of 400 rpm, for 2 h to obtain a slurry, and filter, wash, and dry to obtain a powder.

[0060] S2: The powder described in S1 is calcined at 850°C for 8 hours in an air atmosphere to obtain a novel lithium ion sieve precursor material. (3) Lithium removal:

[0061] The novel lithium ion sieve precursor material described in step (2) is soaked in a 0.7M hydrochloric acid solution to complete lithium deintercalation, filtered and dried to obtain a novel lithium ion sieve.

[0062] Example 4

[0063] This embodiment provides a novel lithium ion sieve preparation method for extracting lithium from produced water in oil and gas fields, comprising the following specific steps:

[0064] (1) Preparation of lithium ion sieve precursor:

[0065] S1: 1.3 g of manganese carbonate and 1 g of lithium hydroxide were uniformly mixed in advance and ball-milled to micron size.

[0066] S2: Dissolve in deionized water, place the mixed solution in a magnetic stirrer and stir at a speed of 600 rpm, a temperature of 40°C, and a time of 2 hours. During the stirring process, slowly add 4 ml of a 30% hydrogen peroxide solution. S3: Filter and dry to obtain a mixed powder.

[0067] S4: calcining the powder in S3 at 450° C. for 7 h in an air atmosphere to obtain a lithium ion sieve precursor material.

[0068] (2) Surface modification:

[0069] S1: Mix 1 g of the lithium ion sieve precursor material synthesized in step (1), 1.2 g of lanthanum nitrate, and 7 ml of ammonia water for reaction, stir at 25°C, at a speed of 400 rpm, for 2 h to obtain a slurry, filter, wash, and dry to obtain a powder.

[0070] S2: The powder described in S1 was calcined at 850°C for 10 hours in an air atmosphere to obtain a new lithium ion sieve precursor material.

[0071] (3) Lithium removal:

[0072] The novel lithium ion sieve precursor material of step (2) is soaked in a 0.8M hydrochloric acid solution to complete lithium deintercalation, filtered and dried to obtain the novel lithium ion sieve.

[0073] Example 5

[0074] This embodiment provides a novel lithium ion sieve preparation method for extracting lithium from produced water in oil and gas fields, comprising the following specific steps:

[0075] (1) Preparation of lithium ion sieve precursor:

[0076] S1: 1.2 g of manganese carbonate and 1 g of lithium hydroxide were uniformly mixed in advance and ball-milled to micron size.

[0077] S2: Dissolve in deionized water, place the mixed solution in a magnetic stirrer and stir at a speed of 600 rpm, a temperature of 40°C, and a time of 2 hours. During the stirring process, slowly add 4 ml of a 30% hydrogen peroxide solution. S3: Filter and dry to obtain a mixed powder.

[0078] S4: calcining the powder in S3 at 450° C. for 7 h in an air atmosphere to obtain a lithium ion sieve precursor material.

[0079] (2) Surface modification:

[0080] S1: Mix 1 g of the lithium ion sieve precursor material synthesized in step (1), 1.1 g of lanthanum nitrate, and 8 ml of ammonia water for reaction, stir at 45°C, at a speed of 500 rpm, for 2 h to obtain a slurry, and filter, wash, and dry to obtain a powder.

[0081] S2: The powder described in S1 was calcined at 850°C for 15 hours in an air atmosphere to obtain a new lithium ion sieve precursor material.

[0082] (3) Lithium removal:

[0083] The novel lithium ion sieve precursor material described in step (2) is soaked in a 1.0M hydrochloric acid solution to complete lithium deintercalation, filtered and dried to obtain the novel lithium ion sieve.

[0084] Test Example 1

[0085] The preparation process stops at step (1), where the lithium ion sieve precursor material is obtained, and the lithium ion sieve is obtained by soaking in hydrochloric acid and drying, and then subjected to a comparative adsorption test with the surface-modified new ion sieve in a lithium-containing solution (concentration of 150 mg / L). Lithium adsorption capacity calculation method: adsorption capacity = (adsorption tail liquid lithium ion concentration - original solution lithium ion concentration) * solution volume / ion sieve mass.

[0086] The experimental results are shown in Table 1:

[0087] Table 1 Lithium adsorption capacity

[0088]

[0089] It can be seen from Table 1 that the novel lithium ion sieve prepared by the present invention can effectively improve the recovery rate of lithium.

[0090] Test Example 2

[0091] The lithium extraction experiment was conducted on the produced water from the actual oil and gas field. The water sample came from the stock solution of Deyang, Sichuan. The adsorption capacity comparison experiment was conducted with reference to Experimental Example 1. Table 2 shows the components of the stock solution of Deyang, Sichuan.

[0092] Table 2 Lithium adsorption capacity (actual stock solution)

[0093] Components Li Na Ca K Mg Ba Concentration (mg / L) 158.6 38.90 2.008 4137.5 190.3 332.37

[0094] The comparative experimental results are shown in Table 3:

[0095] Table 3 Lithium adsorption capacity (actual stock solution)

[0096]

[0097] Table 3 shows the feasibility of the novel lithium ion sieve prepared in the present invention in extracting lithium from produced water in oil and gas fields.

[0098] Test Example 3

[0099] Referring to Experiment 2, the manganese loss rates of the lithium ion sieve and the new lithium ion sieve were measured, and the calculation method was: manganese loss rate = (1-manganese content of adsorption tail liquid / manganese content of ion sieve) * 100%.

[0100] Table 4 Manganese loss rate (actual original solution)

[0101]

[0102] It can be seen from Table 4 that the new lithium ion sieve with rare earth metal surface modification significantly reduces the problem of manganese dissolution loss during the circulation of the lithium ion sieve, and can be effectively used in the lithium extraction process of produced water in oil and gas fields.

[0103] Obviously, the above embodiments are only used to illustrate the specific implementation of the present invention, and are not intended to limit the implementation. For those skilled in the art, other different forms of adjustments or improvements can be made based on the understanding of the present invention. In this field, it is not necessary and impossible to list all possible implementations. Any obvious changes or adjustments still fall within the scope of protection of the present invention.

Claims

1. A method for preparing a novel lithium ion sieve for extracting lithium from produced water in oil and gas fields, characterized in that: The following steps are involved: S1: mixing a manganese source and a lithium source, stirring, and adding an oxidant to form a manganese-lithium mixed solution, filtering the manganese-lithium mixed solution through precipitation to obtain a primary filter cake and a primary filtrate, washing with water for multiple times, and drying to form a solid mixture; performing a first calcination in a muffle furnace to synthesize an ion sieve precursor material having a spinel structure; S2: The ion sieve precursor material obtained in S1 is uniformly mixed with a water-soluble lanthanum salt, and a precipitant is used and injected into a reaction container. After the reaction is completed, the reactants are repeatedly precipitated, washed, and filtered, placed in a vacuum drying oven, and placed in a muffle furnace for a second calcination to obtain a novel lithium ion sieve precursor; S3: S2 is calcined to obtain a novel lithium ion sieve precursor, which is then soaked in an inorganic acid solution, filtered and dried to obtain a novel lithium ion sieve.

2. A method for preparing a novel lithium ion sieve for extracting lithium from produced water in oil and gas fields according to claim 1, characterized in that: The manganese source is manganese carbonate, manganese chloride or manganese sulfate; the lithium source is lithium hydroxide, lithium chloride or lithium carbonate; and the water-soluble lanthanum salt is lanthanum chloride or lanthanum nitrate.

3. A method for preparing a novel lithium ion sieve for extracting lithium from produced water in oil and gas fields according to claim 1, characterized in that: The mass ratio of manganese source to lithium source is (1-1.5):

1.

4. A method for preparing a novel lithium ion sieve for extracting lithium from produced water in oil and gas fields according to claim 1, characterized in that: In S1, the mixture is washed with water several times until the pH of the filtrate is between 7.2 and 8.

5. A method for preparing a novel lithium ion sieve for extracting lithium from produced water in oil and gas fields according to claim 1, characterized in that: During the stirring in S1, hydrogen peroxide is used as an oxidant, and the amount of hydrogen peroxide used is 3-5% of the volume of the manganese-lithium mixed solution, and is added slowly to prevent overflow; During the stirring and mixing in S1, the stirring speed is 400-600 rpm, the temperature is 25-45° C., and the time is 1-4 h.

6. The method for preparing a novel lithium ion sieve for extracting lithium from produced water in oil and gas fields according to claim 1, characterized in that: In S1, the first calcination is carried out in a muffle furnace at a calcination temperature of 450°C-500°C and a calcination time of 7-8h.

7. A method for preparing a novel lithium ion sieve for extracting lithium from produced water in oil and gas fields according to claim 1, characterized in that: In S2, the precipitant is ammonia water, and the amount of ammonia water used is 5-8% of the volume of the mixed solution.

8. The method for preparing a novel lithium ion sieve for extracting lithium from produced water in oil and gas fields according to claim 1, characterized in that: The mixture of the water-soluble lanthanum salt and the ion sieve precursor material in step S1 is ball-milled until the particle size reaches micrometer level; the mass ratio of the water-soluble lanthanum salt to the ion sieve precursor material in step S1 is (1.5-3):

1.

9. A method for preparing a novel lithium ion sieve for extracting lithium from produced water in oil and gas fields according to claim 1, characterized in that: In S2, the second calcination is carried out in a muffle furnace, the calcination temperature is set at 750°C-900°C, and the calcination time is 8-15h.

10. A method for preparing a novel lithium ion sieve for extracting lithium from produced water in oil and gas fields according to claim 1, characterized in that: The inorganic acid in S3 is hydrochloric acid, sulfuric acid or nitric acid; the concentration of the inorganic acid is 0.5-1M, and the mass ratio of the novel lithium ion sieve to the inorganic acid solution is 1:(60-100).

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