阅读说明：本技术 一种利用油页岩半焦或油页岩灰分级提取多种产品的方法 (Method for extracting various products by utilizing oil shale semicoke or oil shale ash in grading manner ) 是由 郭洪范 王卓 刘云义 熊莉佳 窦泽伟 王志远 于 2021-09-15 设计创作，主要内容包括：本发明公开了一种利用油页岩半焦或油页岩灰分级提取多种产品的方法,包括：收集油页岩半焦或油页岩灰作为原料,原料经粉碎后备用；利用粉碎后的原料提取碳酸钙产品和/或二氧化硅产品。本发明可使油页岩固体废弃物中的钙、硅等成分实现有效分离,同时获得碳酸钙和二氧化硅(白炭黑)等产品,同时工艺物料可循环,中间产物铵溶液、氨气实现循环使用,产生的二氧化碳回收并高值化利用,提取剩余的废渣也可用于建筑材料和提铝原料等领域,基本没有三废排放,环境效益显著。(The invention discloses a method for extracting various products by utilizing oil shale semicoke or oil shale ash in a grading way, which comprises the following steps: collecting oil shale semi-coke or oil shale ash as a raw material, and crushing the raw material for later use; and extracting a calcium carbonate product and/or a silicon dioxide product by using the crushed raw materials. The method can effectively separate the calcium, the silicon and other components in the oil shale solid waste, simultaneously obtain the products of calcium carbonate, silicon dioxide (white carbon black) and the like, simultaneously recycle the process materials, recycle the intermediate product ammonium solution and the ammonia gas, recycle and highly utilize the generated carbon dioxide, extract the residual waste residue, can also be used in the fields of building materials, aluminum extraction raw materials and the like, basically has no three-waste discharge, and has remarkable environmental benefit.)

1. A method for extracting various products by utilizing oil shale semicoke or oil shale ash in a grading way is characterized by comprising the following steps:

s1, collecting oil shale semi-coke or oil shale ash as a raw material, and crushing the raw material for later use;

s2, extracting a calcium carbonate product and/or a silicon dioxide product by using the crushed raw materials.

2. The method for extracting multiple products by using oil shale semicoke or oil shale ash in a grading manner according to claim 1, wherein in the step S2, when only calcium carbonate products are extracted, the specific steps are as follows:

S2A1, placing the crushed raw materials in a calcining furnace for calcining treatment to obtain calcined powder, and recovering carbon dioxide gas generated in the calcining process;

S2A2, adding the calcined powder prepared in the step S2A1 into a circulating mother liquor A, heating to carry out ammonia evaporation reaction, recovering the generated ammonia gas into an ammonia gas collecting tank, and filtering after the reaction is finished to obtain a filtrate A rich in water-soluble calcium salt and a solid residue I after calcium extraction;

S2A3, introducing the carbon dioxide gas obtained in the step S2A1 and the ammonia gas obtained in the step S2A2 into the filtrate A rich in water-soluble calcium salt, and adding Ca²⁺And (3) carrying out precipitation reaction on ions, wherein the precipitate is calcium carbonate, filtering the reaction solution after the reaction is finished, and collecting filter residues to obtain a calcium carbonate product.

3. The method for extracting multiple products by using oil shale semicoke or oil shale ash in a grading manner according to claim 1, wherein in the step S2, when only silica products are extracted, the specific steps are as follows:

S2B1, placing the crushed raw materials into a calcining furnace for calcining to obtain calcined powder or directly adding the crushed raw materials into a circulating mother liquor B for ammonia distillation extraction reaction, recovering the released ammonia gas into an ammonia gas collecting tank, and filtering after the reaction is finished to obtain filtrate B and solid residues II, wherein the filtrate B is a solution rich in Si compounds;

and S2B2, introducing the ammonia gas obtained in the step S2B1 into the filtrate B to obtain silicon dioxide precipitate, filtering after the reaction is finished, and collecting filter residues, namely the silicon dioxide product.

4. The method for extracting various products by using oil shale semi-coke or oil shale ash in a grading way according to claim 1, wherein the specific steps for extracting the calcium carbonate product and the silica product in the step S2 are as follows:

S2C1, placing the crushed raw materials into a calcining furnace for calcining treatment to obtain calcined powder, and recovering carbon dioxide gas generated in the calcining process;

S2C2, adding the calcined powder prepared in the step S2C1 into a circulating mother liquor A, heating to carry out ammonia evaporation reaction, recovering the generated ammonia gas into an ammonia gas collecting tank, and filtering after the reaction is finished to obtain a filtrate A rich in water-soluble calcium salt and a solid residue I after calcium extraction;

S2C3, adding the solid residue I obtained in the step S2C2 into a circulating mother liquor B, performing ammonia evaporation extraction reaction, recovering released ammonia gas into an ammonia gas collecting tank, and filtering after the reaction is finished to obtain a filtrate B and a solid residue II, wherein the filtrate B is a solution rich in Si compounds;

S2C4, introducing the carbon dioxide gas obtained in the step S2C1 and the ammonia gas obtained in the step S2C2 into a filtrate A rich in water-soluble calcium salt, and adding Ca²⁺Carrying out precipitation reaction on ions, wherein the precipitate is calcium carbonate, filtering a reaction solution after the reaction is finished, and collecting filter residues, namely a calcium carbonate product;

and S2C5, introducing the ammonia gas obtained in the step S2C3 into the filtrate B to obtain silicon dioxide precipitate, filtering after the reaction is finished, and collecting filter residues, namely the silicon dioxide product.

5. The method for fractional extraction of various products using oil shale semicoke or oil shale ash according to claim 2 or 4, wherein: the circulating mother liquor A is an aqueous solution containing ammonium chloride or ammonium nitrate or ammonium acetate.

6. The method for fractional extraction of various products using oil shale semicoke or oil shale ash according to claim 3 or 4, wherein: the circulating mother liquor B is an aqueous solution containing ammonium fluoride.

7. The method for fractional extraction of multiple products from oil shale semicoke or oil shale ash according to any one of claims 2 to 4, wherein: the ammonia distillation reaction is carried out at 85-105 ℃.

8. The method of claim 2 or 4, wherein the oil shale semicoke or oil shale ash is used for fractional extractionThe method for taking various products is characterized by comprising the following steps: the Ca²⁺The ion precipitation reaction is carried out at 40-120 deg.C.

9. The method for fractional extraction of various products using oil shale semicoke or oil shale ash according to claim 3 or 4, wherein: the silica precipitation is carried out at 40-90 ℃.

Technical Field

The invention relates to the field of comprehensive utilization of oil shale resources, in particular to a method for extracting various products by utilizing oil shale semicoke or oil shale ash in a grading manner.

Background

The oil shale is a sedimentary rock containing combustible organic matter, and the organic matter contained in the sedimentary rock can be converted into shale oil similar to crude oil through dry distillation, or can be used as solid fuel to directly burn, generate heat (generate steam) and generate electricity, which are two main development directions of the oil shale industry.

The oil shale resource reserves are huge and are listed as one of the most important alternative energy sources in the 21 st century, but the development of the oil shale industry has a huge bottleneck. The oil shale is retorted and refined to produce oil shale semicoke, and is directly combusted to produce oil shale ash, the amount of the solid byproducts is extremely large, because the inorganic substance content in the oil shale is very high, the solid byproducts are high-ash solid fuel, and for example, about 10-30 tons of solid waste can be simultaneously generated when 1 ton of shale oil is refined. However, the utilization rate of the solid by-product in the oil shale industry is not high, and the solid by-product is generally piled as waste at present and rarely used, so that not only a large amount of land is occupied, but also the environment is seriously polluted, for example, the oil shale semicoke contains water-soluble phenolic compounds, sulfur-containing compounds, semi-volatile substances, polycyclic aromatic hydrocarbons and other toxic pollutants, and the exudate formed in the dumping and open-air placing processes can seriously threaten the underground water.

The development of the oil shale industry is severely restricted by the problem of disposal of solid by-products generated by utilization of oil shale resources. If solid waste in the oil shale industry can be used as a raw material to prepare a product with a high added value, the economical efficiency of oil shale resource utilization can be improved, the problem of environmental pollution can be effectively solved, and the comprehensive utilization of resources without solid waste discharge can be realized.

Therefore, it is urgently needed to develop a utilization method of oil shale semicoke or oil shale ash to solve the above problems.

Disclosure of Invention

The invention aims to solve the problems in the prior art and provides a method for extracting various products by utilizing oil shale semicoke or oil shale ash in a grading manner.

In order to achieve the purpose, the invention is implemented according to the following technical scheme:

a method for extracting various products by utilizing oil shale semicoke or oil shale ash in a grading way comprises the following steps:

s1, collecting oil shale semi-coke or oil shale ash as a raw material, and crushing the raw material for later use;

s2, extracting a calcium carbonate product and/or a silicon dioxide product by using the crushed raw materials.

Further, in the step S2, when only the calcium carbonate product is extracted, the specific steps are as follows:

S2A1, placing the crushed raw materials in a calcining furnace for calcining treatment to obtain calcined powder, and recovering carbon dioxide gas generated in the calcining process;

S2A2, adding the calcined powder prepared in the step S2A1 into a circulating mother liquor A, heating to carry out ammonia evaporation reaction, recovering the generated ammonia gas into an ammonia gas collecting tank, and filtering after the reaction is finished to obtain a filtrate A rich in water-soluble calcium salt and a solid residue I after calcium extraction;

S2A3, introducing the carbon dioxide gas obtained in the step S2A1 and the ammonia gas obtained in the step S2A2 into the filtrate A rich in water-soluble calcium salt, and adding Ca²⁺And (3) carrying out precipitation reaction on ions, wherein the precipitate is calcium carbonate, filtering the reaction solution after the reaction is finished, and collecting filter residues to obtain a calcium carbonate product.

Further, in the step S2, when only the silica product is extracted, the specific steps are as follows:

S2B1, placing the crushed raw materials into a calcining furnace for calcining to obtain calcined powder or directly adding the crushed raw materials into a circulating mother liquor B for ammonia distillation extraction reaction, recovering the released ammonia gas into an ammonia gas collecting tank, and filtering after the reaction is finished to obtain filtrate B and solid residues II, wherein the filtrate B is a solution rich in Si compounds;

and S2B2, introducing the ammonia gas obtained in the step S2B1 into the filtrate B to obtain silicon dioxide precipitate, filtering after the reaction is finished, and collecting filter residues, namely the silicon dioxide product.

Further, in the step S2, when extracting the calcium carbonate product and the silica product, the specific steps are as follows:

S2C1, placing the crushed raw materials into a calcining furnace for calcining treatment to obtain calcined powder, and recovering carbon dioxide gas generated in the calcining process;

S2C2, adding the calcined powder prepared in the step S2C1 into a circulating mother liquor A, heating to carry out ammonia evaporation reaction, recovering the generated ammonia gas into an ammonia gas collecting tank, and filtering after the reaction is finished to obtain a filtrate A rich in water-soluble calcium salt and a solid residue I after calcium extraction;

S2C3, adding the solid residue I obtained in the step S2C2 into a circulating mother liquor B, performing ammonia evaporation extraction reaction, recovering released ammonia gas into an ammonia gas collecting tank, and filtering after the reaction is finished to obtain a filtrate B and a solid residue II, wherein the filtrate B is a solution rich in Si compounds;

S2C4, introducing the carbon dioxide gas obtained in the step S2C1 and the ammonia gas obtained in the step S2C2 into a filtrate A rich in water-soluble calcium salt, and adding Ca²⁺Carrying out precipitation reaction on ions, wherein the precipitate is calcium carbonate, filtering a reaction solution after the reaction is finished, and collecting filter residues, namely a calcium carbonate product;

and S2C5, introducing the ammonia gas obtained in the step S2C3 into the filtrate B to obtain silicon dioxide precipitate, filtering after the reaction is finished, and collecting filter residues, namely the silicon dioxide product.

Further, the circulating mother liquor A is an aqueous solution containing ammonium chloride or ammonium nitrate or ammonium acetate.

Further, the circulating mother liquor B is an aqueous solution containing ammonium fluoride.

Further, the ammonia distillation reaction is carried out at 85-105 ℃.

Further, the Ca²⁺The ion precipitation reaction is carried out at 40-120 deg.C.

Further, the silica precipitation is carried out at 40-90 ℃.

Compared with the prior art, the method can effectively separate calcium, silicon and other components in the oil shale solid waste, simultaneously obtain products such as calcium carbonate and silicon dioxide (white carbon black), simultaneously process materials can be recycled, the intermediate products ammonium solution and ammonia gas can be recycled, the generated carbon dioxide can be recovered and utilized in a high-value manner, finally the residual waste residue can also be used in the fields such as building materials, and the like, basically no three wastes are discharged, and the environmental benefit is obvious; in addition, the method for extracting the oil shale semicoke or the oil shale ash in a grading manner not only realizes high-value utilization of a large amount of solid wastes and avoids serious problems of resource waste, large land occupation, environmental pollution and the like, but also has strong adaptability of raw materials of the process, can flexibly regulate and control reaction steps according to the components of the oil shale industrial solid wastes, and further realizes flexible regulation and control of the types of process products.

Drawings

Fig. 1 is a schematic diagram of the distribution of the working sections of the oil shale semicoke or oil shale ash fractional extraction method of the present invention.

FIG. 2 is a detailed flow chart of the method of the present invention.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. The specific embodiments described herein are merely illustrative of the invention and do not limit the invention.

Example 1

When the collected oil shale semicoke or oil shale ash has very low silicon content and no need of extracting silicon, only calcium carbonate products need to be extracted, as shown in fig. 1 and fig. 2, the embodiment provides a method for extracting various products by using oil shale semicoke or oil shale ash in a grading way, and the method comprises the following steps:

s1, collecting oil shale semi-coke or oil shale ash as a raw material, and crushing the raw material for later use;

S2A1, placing the crushed raw materials into a calcining furnace for calcining treatment, controlling the temperature at 850-1100 ℃, calcining for 1-2 hours to obtain calcined powder, and recovering carbon dioxide gas generated in the calcining process;

S2A2, adding the calcined powder prepared in the step S2A1 into a circulating mother liquor A (in the embodiment, the circulating mother liquor A uses an aqueous solution containing ammonium chloride), wherein NH in the aqueous solution containing ammonium chloride₄Performing ammonia distillation reaction at 85-105 ℃ with the Cl concentration of 1.0-2.0mol/L, recovering the generated ammonia gas into an ammonia gas collecting tank, and filtering after the reaction is finished to obtain filtrate A rich in water-soluble calcium salt and solid residue I after calcium extraction;

S2A3, introducing the carbon dioxide gas obtained in the step S2A1 and the ammonia gas obtained in the step S2A2 into the filtrate A rich in the water-soluble calcium salt, and stirring at the speed of 200-1000rpm and the temperature of 40-120 ℃ under Ca²⁺And (3) carrying out precipitation reaction on ions, wherein the precipitate is calcium carbonate, filtering the reaction solution after the reaction is finished, wherein the filtrate is a circulating mother solution A and is circularly used in the step S2A2, and the collected filter residue is washed, filtered, dried and ground to obtain a calcium carbonate powder product.

Example 2

When the collected shale semicoke or oil shale ash has low calcium content and no need of extracting silicon, only a silicon dioxide product needs to be extracted, as shown in fig. 1 and fig. 2, the embodiment provides a method for extracting various products by using oil shale semicoke or oil shale ash in a grading way, and the method comprises the following steps:

s1, collecting oil shale semi-coke or oil shale ash as a raw material, and crushing the raw material for later use;

S2B1, placing the crushed raw materials into a calcining furnace for calcining treatment (850-1100 ℃ for 1-2 hours) to obtain calcined powder or directly adding the crushed raw materials into circulating mother liquor B (in the embodiment, the circulating mother liquor B uses an aqueous solution containing ammonium fluoride), performing ammonia distillation extraction reaction at 85-105 ℃, recovering released ammonia into an ammonia gas collecting tank, and filtering after the reaction to obtain filtrate B and solid residue II, wherein the filtrate B is a compound rich in Si (such as (NH) and is rich in Si compounds (such as (NH) and (C)₄)SiF₆State present);

and S2B2, introducing the ammonia gas obtained in the step S2B1 into the filtrate B, reacting at 40-90 ℃ to obtain silicon dioxide precipitate, filtering after the reaction is finished, wherein the filtrate is circulating mother liquor B and can be circularly used in the S2B1, and the filter residue is silicon dioxide, and washing, filtering, drying and grinding are carried out to obtain a silicon dioxide powdery product.

Example 3

When the collected oil shale semicoke or oil shale ash contains calcium and silicon which need to be extracted, as shown in fig. 1 and fig. 2, the embodiment provides a method for extracting various products by using oil shale semicoke or oil shale ash in a grading way, which comprises the following steps:

s1, collecting oil shale semi-coke or oil shale ash as a raw material, and crushing the raw material for later use;

S2C1, placing the crushed raw materials into a calcining furnace for calcining treatment, controlling the temperature at 850-1100 ℃, calcining for 1-2 hours to obtain calcined powder, and recovering carbon dioxide gas generated in the calcining process;

S2C2, adding the calcined powder obtained in the step S2C1 into a circulating mother liquor A (in the embodiment, an ammonium chloride-containing aqueous solution is used as the circulating mother liquor A), wherein NH in the ammonium chloride-containing aqueous solution₄Performing ammonia distillation reaction at 85-105 ℃ with the Cl concentration of 1.0-2.0mol/L, recovering the generated ammonia gas into an ammonia gas collecting tank, and filtering after the reaction is finished to obtain filtrate A rich in water-soluble calcium salt and solid residue I after calcium extraction;

S2C3, adding the solid residue I obtained in the step S2C2 into a circulating mother liquor B (in the embodiment, the circulating mother liquor B uses ammonium salt aqueous solution containing ammonium fluoride), performing ammonia distillation extraction reaction at 85-105 ℃, recovering released ammonia gas into an ammonia gas collecting tank, and filtering after the reaction is finished to obtain a filtrate B and a solid residue II, wherein the filtrate B is a compound (containing (NH) rich in Si₄)SiF₆State present);

S2C4, introducing the carbon dioxide gas obtained in the step S2C1 and the ammonia gas obtained in the step S2C2 into the filtrate A rich in the water-soluble calcium salt, and stirring at the speed of 200-1000rpm and the temperature of 40-120 ℃ under Ca²⁺Carrying out precipitation reaction on ions, wherein the precipitate is calcium carbonate, filtering the reaction solution after the reaction is finished, wherein the filtrate is a circulating mother liquor A and is circularly used in the step S2C2, and the collected filter residue is washed, filtered, dried and ground to obtain a calcium carbonate powder product;

and S2C5, introducing the ammonia gas obtained in the step S2C3 into the filtrate B, reacting at 40-90 ℃ to obtain silicon dioxide precipitate, filtering after the reaction is finished, wherein the filtrate is circulating mother liquor B and can be circularly used in the S2C3, and the filter residue is silicon dioxide, and washing, filtering, drying and grinding are carried out to obtain a silicon dioxide powdery product.

For example 1, example 2 and example 3, the number of times of extracting ammonium chloride can be increased appropriately according to the difficulty and composition of extracting different components of the solid waste in the oil shale industry, and the selection between the extraction effect and the cost of ammonium chloride can be made.

In addition, in the above embodiment, the solid residue after the process extraction in the steps S2a2, S2B1, or S2C3, and the impurities such as Al, Mg, etc. in the steps S2A3, S2B2, S2C4, or S2C5, which can be removed (precipitated) by adjusting the pH of the circulating mother liquor, can be used as building materials or aluminum smelting raw materials, etc. to reduce the discharge of process wastes and further increase the utilization rate of resources.

The principle of the method for extracting and preparing various high value-added products by using solid waste in the oil shale industry as raw materials in a grading way is as follows: firstly, the oil shale semicoke or oil shale ash is calcined to remove organic matters and carbon components in the raw materials and prevent the organic matters and the carbon components from reducing subsequent CaCO₃And SiO₂Etc. of the product, and the calcium carbonate is decomposed into calcium oxide and CO₂Gas (reaction equation: CaCO)₃→CaO+CO₂×) in the solid raw material, calcium carbonate is converted into calcium oxide to facilitate subsequent extraction of calcium element from the solid raw material; then the calcined raw material reacts with ammonium salt solution in a grading way, the selectivity of ammonium salt is regulated and controlled to react with different components in the oil shale solid waste raw material in a grading way by regulating and controlling the composition of ammonium salt anions, firstly, the ammonium salt (circulating mother liquor A) reacts with calcium oxide (first extraction, and the reaction equation is that CaO + H₂O→Ca(OH)₂And Ca (OH)₂+2NH₄Cl→2NH₃↑+CaCl₂+2H₂O，NH₄Cl may also be replaced by NH₄NO₃And NH₄Ac), and further adding water-soluble Ca to calcium element in the solid raw material²⁺The ions are extracted into the aqueous solution, ammonia gas is released and recovered,filtering to obtain Ca²⁺Filtering the ionic filtrate and the calcium-removed oil shale solid waste residues, and then carrying out the reaction on the obtained carbon dioxide and NH₃Introduction of gas into Ca²⁺Preparation of calcium carbonate in solution under alkaline condition (reaction equation: Ca)²⁺+2NH₃+H₂O+CO₂→CaCO₃↓+2NH₄ ⁺) Filtering the reaction solution to obtain a calcium carbonate product, wherein the filtrate is a circulating mother solution A, and the newly obtained circulating mother solution A is recycled; then extracting silicon component in the oil shale solid waste for the second time, adding the filter residue obtained after the first extraction into another ammonium salt solution (circulating mother liquor B), carrying out ammonia distillation reaction for the second time, recovering the evaporated ammonia gas, and filtering to obtain the product rich in water-soluble silicon compound (SiF)₆ ^-) Then introducing ammonia gas into the obtained filtrate rich in the silicon compound to prepare silicon dioxide, wherein the filtrate obtained by filtering is the circulating mother liquor B for recycling, and the filter residue is a silicon dioxide product; in the above reaction, the ammonium salt is passed over NH₄ ⁺→NH₃↓ [ sic ] and the inverse process NH thereof₃↑→NH₄ ⁺Recycling of CO₂The gas is recycled, the solid residues such as components and the like which cannot be extracted from the raw materials can be used as building materials, aluminum-smelting raw materials and the like, the process basically generates no by-products, and the reaction process is green.

The technical solution of the present invention is not limited to the limitations of the above specific embodiments, and all technical modifications made according to the technical solution of the present invention fall within the protection scope of the present invention.