CN-121974970-A - Alkaline desulfurization and denitrification agent and application thereof in flue gas recycling desulfurization and denitrification process coupled coal-rock gas acidification yield increase and injection increase

CN121974970ACN 121974970 ACN121974970 ACN 121974970ACN-121974970-A

Abstract

The invention relates to the fields of resource utilization of flue gas purification products and yield and injection increase of coal and rock gas, in particular to an alkaline desulfurization and denitrification agent and application thereof in flue gas resource desulfurization and denitrification technology coupling coal and rock gas acidification yield and injection increase. The invention provides an alkaline desulfurization and denitrification agent which contains a sasanqua saponin and a crown ether ring structure, sulfuric acid, nitric acid and fluoboric acid mixed salt of the alkaline desulfurization and denitrification agent is generated after desulfurization and denitrification, the mixed salt is used for acidizing coal and rock gas, so that flue gas desulfurization and denitrification waste liquid can be recycled, desulfurization and denitrification cost can be recovered, in addition, the flue gas desulfurization and denitrification can be carried out by combining the crown ether and sasanqua saponin-containing bisimidazoline alkaline desulfurization and denitrification agent with plasma irradiation oxidation, and the desulfurization and denitrification waste liquid is used for reservoir reconstruction, so that environmental pollution can be better treated, the cost of carbonate reservoir acidification can be reduced, and retarded acidification and steering acidification can be realized.

Inventors

MA JIANMIN
ZHANG CHAO
LI BINGLIN
MA SHAOHUA
LIU DONGDONG
ZHANG XIAOYANG
SU YULIANG
FAN JIABAO
LI PENGFEI
LI BINFEI

Assignees

中国石油大学(华东)
青岛中石大教育发展有限公司
石河子大学

Dates

Publication Date: 20260505
Application Date: 20260130

Claims (10)

1. An alkaline desulfurization and denitrification agent is characterized in that the alkaline desulfurization and denitrification agent is [ M ] [ BF 4 ] 2 ] with the chemical formula: ; Wherein, the R 1 is triterpene mother nucleus of sasanqua saponin, and the structural formula is: ; G 1 、G 2 is two glycosidic chains attached to the glycosidic unit.
2. The alkaline desulfurization and denitrification agent according to claim 1, wherein, The structural formula of the glycosidic chain is as follows: ; 。
3. the alkaline desulfurization and denitrification agent according to claim 1, wherein, The synthesis method of the alkaline desulfurization and denitrification agent comprises the steps of taking triethylene tetramine as a raw material, dropwise adding gallic acid to react to obtain a mono-imidazoline intermediate, sequentially dropwise adding LiOH, pentafluoroethylene glycol and boron trifluoride to react to obtain a mono-quaternized imidazoline intermediate, dropwise adding sasanquasaponin to react to obtain an intermediate containing sasanquasaponin, sequentially dropwise adding pentafluoroethylene glycol and boron trifluoride to react to obtain the alkaline desulfurization and denitrification agent.
4. The alkaline desulfurization and denitrification agent according to claim 3, wherein, The synthesis method of the alkaline desulfurization and denitrification agent comprises the following steps: (1) Adding triethylene tetramine into a reaction kettle, heating to 100-120 ℃, dropwise adding gallic acid according to the mole ratio of triethylene tetramine to gallic acid of 1-1.4, heating to 140-160 ℃ until no water is generated, heating to the reaction temperature of 240-260 ℃ for further reaction for 7-10 hours, and removing byproducts by reduced pressure distillation after the reaction is finished to obtain a mono-imidazoline intermediate, adding LiOH into the mono-imidazoline intermediate according to the mole ratio of the mono-imidazoline intermediate to LiOH of 1 (2-4), stirring in tetrahydrofuran aqueous solution, heating to 70 ℃ for refluxing for 1 hour, adding boron trifluoride according to the mole ratio of the mono-imidazoline intermediate to pentafluoride of 1 (1.6-2.4), dropwise adding boron trifluoride according to the mole ratio of the mono-imidazoline intermediate to boron trifluoride of 0.8-1.2, reacting for 60-80 hours, and maintaining the pH of the solution to 8-10; (2) The preparation method of the alkaline desulfurization and denitrification agent comprises the steps of taking a mono-quaternized imidazoline intermediate, heating to 100-120 ℃, dropwise adding the tea saponin according to the molar ratio of the mono-imidazoline to the tea saponin of 1-1.4, heating to 150 ℃ until no water is generated, heating to the reaction temperature of 240-260 ℃ for continuous reaction for 7-10 hours, reducing pressure and distilling off byproducts after the reaction is finished to obtain the tea saponin-containing intermediate, heating in a constant-temperature water bath at 90 ℃ by using isopropanol, dropwise adding the pentafluoroethylene glycol under stirring, dropwise adding boron trifluoride, wherein the molar ratio of the oil-containing tea saponin intermediate, the pentafluoroethylene glycol and the boron trifluoride is 1 (0.9-1.1), reacting for 1 hour after boron trifluoride dropwise adding is completed, stirring and distilling under reduced pressure to obtain the alkaline desulfurization and denitrification agent.
5. Use of the alkaline desulfurization and denitrification agent according to any one of claims 1-4 in flue gas recycling desulfurization and denitrification process coupled with coal gas acidification, production and injection enhancement, wherein the application method comprises flue gas desulfurization and denitrification process and coal gas acidification, production and injection enhancement process: (1) Flue gas desulfurization and denitration process: the flue gas is subjected to desulfurization and denitrification by the 1 st, 2 nd, 3 rd and 4 th stages of reactors in sequence, Wherein, in the 1 st stage reactor and the 3 rd stage reactor, SO x 、NO x in the flue gas is oxidized by ozone under the irradiation of plasma; spraying alkaline desulfurization and denitrification agent solution into the flue gas in the reverse direction of the flow of the flue gas in the 2 nd-stage reactor and the 4 th-stage reactor to obtain waste liquid, and collecting the waste liquid generated by desulfurization and denitrification after the pH of the waste liquid reaches 6-6.5; the waste liquid generated in the 2 nd stage is waste liquid 1, and the waste liquid generated in the 4 th stage is waste liquid 2; (2) The process for increasing the production and injection of the gas acidizing of the coal rock comprises the following steps: sequentially injecting slugs 1 and 2 from far to near to the oil well to increase the production and injection; Wherein, slug 1 is waste liquid 2, and slug 2 is waste liquid 1.
6. The use according to claim 5, wherein, The alkaline desulfurization and denitrification agent solution is an alkaline desulfurization and denitrification agent aqueous solution with the mass fraction of 0.01-0.03wt%.
7. The use according to claim 5, wherein, The air heat exchange tubes are arranged in the 2 nd and 4 th stage reactors, and air sequentially flows through the air heat exchange tubes in the 4 th and 2 nd stage reactors and finally enters the boiler.
8. The use according to claim 5, wherein, The energy density of the plasma irradiation is 10-20W/cm, and the ozone concentration is 300-400 ppm.
9. The use according to claim 5, wherein, In the slug 1, 10-50 m 3 of oil layers per meter; in the slug 2, each meter of oil layer is 20-100 m 3 ; The injection flow rate of each slug is 100-250L/min.
10. The use according to claim 5, wherein, The waste liquid 2 contains 0.010-0.025% of mixed salt of nitric acid and fluoboric acid of [ H 2 M] 4+ ], and the waste liquid 1 contains 0.010-0.025% of mixed salt of nitric acid, sulfuric acid and fluoboric acid of [ H 2 M] 4+ .

Description

Alkaline desulfurization and denitrification agent and application thereof in flue gas recycling desulfurization and denitrification process coupled coal-rock gas acidification yield increase and injection increase Technical Field The invention relates to the fields of resource utilization of flue gas purification products and yield and injection increase of coal and rock gas, in particular to an alkaline desulfurization and denitrification agent and application thereof in flue gas resource desulfurization and denitrification technology coupling coal and rock gas acidification yield and injection increase. Background The flue gas contains NO x、SOx and other pollutant gases, and desulfurization and denitration are needed to control the atmospheric pollution. The desulfurization and denitrification method comprises SCR, SNCR, SCO, an alkali absorption method and an oxidation absorption method. The alkali absorption method is only suitable for NO 2、SO2, but not suitable for NO, the SCO and oxidation absorption method have excellent NO removal effect, but the required oxidant and catalyst have higher cost, are easy to poison when meeting SO 2, the reducing agent and desulfurization and denitrification products of the SCR and SNCR method, such as improper treatment, are easy to cause secondary pollution, and the reaction temperature application window is narrower than that of oxidation and denitrification, and the catalyst has higher cost. Therefore, the research and exploration of the desulfurization and denitrification method which has wide application range, low cost and difficult secondary pollution is an important research subject in the field. The coal rock reservoir minerals are large in brittleness and easy to fracture to generate powder, and conventional fracturing cracks are easy to close, so that holes are formed through acid slick water to achieve the effects of increasing production and injection. In Chinese patent CN116621847A [ H 2Mi]4+ or [ H 2Ms]4+ ] can play a role in acidification, yield increase and injection increase, however, the acid resistance and the salt resistance are low, and the method is difficult to be applied to coal and rock reservoirs. Disclosure of Invention Aiming at the problems, the invention provides an alkaline desulfurization and denitrification agent and application thereof in flue gas recycling desulfurization and denitrification process coupling coal gas acidification, production increase and injection increase, wherein the alkaline desulfurization and denitrification agent is a gemini imidazoline desulfurization and denitrification agent, contains a sasanquasaponin and crown ether ring structure, and generates sulfuric acid, nitric acid and fluoroboric acid mixed salt of the alkaline desulfurization and denitrification agent after desulfurization and denitrification. In addition, the two-stage desulfurization and denitrification of flue gas are carried out by adopting the double imidazoline alkaline desulfurization and denitrification agent containing crown ether and sasanqua saponin and combining plasma irradiation oxidation, the desulfurization and denitrification waste liquid is used for reservoir reconstruction, so that the environmental pollution can be better treated, the cost of acidification of a carbonate reservoir can be reduced, the retarded acidification and the steering acidification can be realized, the problems of the prior art are solved, firstly, the existing desulfurization and denitrification process is limited in application range, high in cost and energy consumption, desulfurization and denitrification products cannot be effectively utilized, secondary pollution is easy to cause, secondly, in the traditional acid fracturing, the acid rock reaction rate is too fast, the action distance is short, the acid slick water is poor in salt tolerance, the acid slick is difficult to enter a dense coal rock reservoir, and therefore, the blockage removal efficiency is low. In order to achieve the above purpose, the present invention adopts the following technical scheme: An alkaline desulfurization and denitrification agent, which is [ M ] [ BF 4]2 ] and has the chemical formula: ; Wherein, the R 1 is triterpene mother nucleus of sasanqua saponin, and the structural formula is: ; G 1、G2 is two glycosidic chains attached to the glycosidic unit. The structural formula of the glycosidic chain is as follows: ; 。 The alkaline desulfurization and denitrification agent is a gemini imidazoline compound, the gemini imidazoline compound contains two quaternary ammonium nitrogen atoms and forms salt with boron fluoric acid, the gemini imidazoline compound also contains two tertiary nitrogen atoms and a crown ether structure, H 2SO4、HNO3 generated by NO x、SOx oxidation can be neutralized during desulfurization and denitrification, and can coordinate with Ca 2+、Mg2+、Al3+、Fe3+ in a reservoir to increase the effect of corrosion bedrock, the gemini imidazoline compound contai