CN-121983170-A - Design method of environment-friendly active carbon efficient formaldehyde removal modified amine impregnating solution

CN121983170ACN 121983170 ACN121983170 ACN 121983170ACN-121983170-A

Abstract

The invention belongs to the field of modified activated carbon, and particularly relates to a design method of an environment-friendly efficient formaldehyde-removing modified amine impregnating solution for activated carbon. The design method comprises the following steps of constructing a radical library of a molecular structure of the impregnating solution, constructing a molecular structure and property constraint condition of a molecular structure model of the impregnating solution, constructing a relational expression of equilibrium adsorption quantity of the impregnating solution molecules on the activated carbon, and a relational expression of theoretical formaldehyde removal capacity of the modified activated carbon obtained after modification of the impregnating solution molecules, and adopting GAMS software as simulation calculation and determining the impregnating solution molecules. According to the method, when molecular structure and property constraint conditions are designed, the safety and environmental performance of the impregnating solution molecules are taken into consideration, so that the obtained impregnating solution has good safety and environmental properties, and the prepared modified activated carbon has excellent formaldehyde removal performance, and the workload of screening the impregnating solution in the traditional test is reduced.

Inventors

XIE YANLI
CAI YUTIAN
SUN XI
YE JIANYUN
XU ZUWEI
ZHANG BINGJIAN
CHEN QINGLIN
ZHANG QI

Assignees

中石化节能技术服务有限公司
中山大学

Dates

Publication Date: 20260505
Application Date: 20251222

Claims (10)

1. The design method of the impregnating solution molecules is characterized by comprising the following steps: s1, constructing a radical library of a molecular structure of the impregnating solution; s2, constructing a molecular structure and property constraint condition of a impregnating solution molecular structure model; s3, constructing a relational expression of equilibrium adsorption quantity of the impregnating solution molecules adsorbed on the activated carbon, and constructing a relational expression of theoretical formaldehyde removal capacity of the modified activated carbon obtained after modification of the impregnating solution molecules; and S4, adopting GAMS software as simulation calculation and determining impregnating solution molecules, wherein the calculation process specifically comprises the steps of constructing a molecular library of a molecular structure model of the impregnating solution based on the molecular structure and property constraint conditions in the step S2, and determining the molecular structure of the impregnating solution from the molecular library based on the relation of the equilibrium adsorption capacity and the relation of the modified activated carbon theoretical formaldehyde removal capacity in the step S3.
2. The method according to claim 1, wherein in the step S1, the radical library of the impregnating solution molecule structure includes an amine group.
3. The method according to claim 1, wherein in step S1, the radical library of the impregnating solution molecule structure is constructed by a radical contribution method.
4. The method according to claim 1, wherein in the step S1, the group library of the impregnating solution molecule structure includes a main chain group set, a functional group set, a chain end group set, a non-chain end group set, an aromatic group set, and a group set containing a carbon-carbon double bond.
5. The method of designing a molecule of an impregnating solution according to claim 4, wherein in step S2, the molecular structure and property constraints include at least one of the following formulas a to e: (a) The constraint equation that the molecular structure can only be one of an acyclic molecule, a monocyclic molecule and a bicyclic molecule is: (1), Wherein, the binary variables y a 、y m and y b respectively represent whether three structures of an acyclic molecule, a monocyclic molecule or a bicyclic molecule exist in the designed molecule; (b) Constraint equations for a molecule with a valence of 0 and a bond between any two adjacent groups that cannot exceed one are respectively: (2), (3); Wherein, formula 2 is a molecular structure constraint equation, formula 3 is a molecular connection mode constraint equation, and N k and v k are the number and valence of groups k in the molecule respectively; (c) The constraint equation imposed on the number of aromatic groups and non-aromatic groups and the manner of connection between them includes: (4), (5); Wherein, the number constraint equation of the aryl group and the non-aryl group in the formula 4, the formula 5 is the connection mode constraint equation of the aryl group and the non-aryl group, G Ar represents the aromatic group set, and N ac is the number of aromatic rings in the molecule; Represents a non-aromatic group set having a valence of 3 or more, Represents an aromatic group set having a valence of 3 or more, wherein AR and NAR represent an aromatic group and a non-aromatic group, respectively, M=y a -y b ,y a and y b are binary variables, when the value of m is-1, 0 or 1, the molecular structure is a bicyclic molecule, a monocyclic molecule or an acyclic molecule respectively; (d) The number of double bond groups in the molecule limits the constraint equation as shown in formula 6: (6); Wherein G D represents a set of groups containing carbon-carbon double bonds; (e) The number limiting equations for the various types of groups include: (7), (8); Wherein formula 7 is a constraint equation of limiting the number of main chain groups in a molecule, formula 8 is a constraint equation of limiting the number of functional groups in a molecule, G M represents a set of main chain groups, G F represents a set of functional groups, and N max represents at most a few groups in a molecule; (f) The designed melting point of the impregnating solution molecules needs to ensure that the impregnating solution is in a liquid state at normal temperature and normal pressure to meet the impregnating requirement, and the property constraint equation is as follows: (9), (10); Wherein, formula 9 is a molecular melting point constraint equation, formula 10 is a molecular boiling point constraint equation, T m,k and T b,k are the contribution values of the group k to the molecular melting point and the boiling point in the group contribution method respectively, T m,0 and T b,0 are constants in the impregnating solution molecular melting point and boiling point estimation model respectively, and T m,max and T b,min represent the maximum value of the impregnating solution molecular melting point and the minimum value of the molecular boiling point respectively; (g) Constraint equation for the flash point of a molecule is as follows formula 11: (11), Wherein F p,k is the contribution value of the group k to the molecular flash point in the group contribution method, and F p,min is the minimum value of the molecular flash point of the impregnating solution required by design; (h) Constraint equations for the water biotoxicity, soil enrichment factor and bioconcentration factor environmental properties of molecules include: (12), (13), (14); Wherein, formula 12 is the constraint equation of molecular water biotoxicity, formula 13 is the constraint equation of molecular soil enrichment factor, formula 14 is the constraint equation of molecular biological concentration factor, LC k 、K ow and BCF k are the contribution values of group k to the molecular water biotoxicity, soil enrichment factor and biological concentration factor of the impregnating solution respectively, LC max 、K oc,max and BCF max are the maximum values of the designed molecular water biotoxicity concentration, soil enrichment factor and biological concentration factor of the impregnating solution respectively; (e) The constraint equation for the number of amine groups in a molecule is as follows formula 15: (15); Wherein N 25 、N 27 、N 28 and N 29 represent the numbers of groups 25, 27, 28, 29 belonging to amino groups, respectively, and 25, 27, 28, and 29 are the numbers of ACNH 2 groups, CH 2 NH 2 groups, CH 3 NH groups, CH 2 NH groups, respectively.
6. The method of designing a molecule of immersion liquid according to claim 5, comprising at least one of: The T m,max is 250-313K; The T b,min is 353K-393K; f p,min is 290-330K; LC max is 1-10mol/L; K oc,max is 10-30; the BCF max is 1-8.
7. The method according to claim 1, wherein in step S3, the equilibrium adsorption amount relationship is represented by the following formula 16: (16); Wherein, the And The mole fraction of component i in the bulk phase and the adsorbed solid solution, respectively; And The activity coefficients of component i in bulk phase and adsorbed solid solution, respectively; is the difference T, R between the chemical potentials of the wetted adsorbent before adsorption and after adsorption of component i The adsorption temperature, the ideal gas constant, and the surface phase capacity of component i, respectively.
8. The method for designing impregnating solution molecules according to claim 1, wherein in step S3, the relation of the theoretical formaldehyde removal ability of the modified activated carbon is as shown in formula 17: (17); Wherein, the Is the saturated adsorption quantity of the activated carbon adsorption molecules, Is the mass of the activated carbon, N 25 、N 27 、N 28 and N 29 respectively represent the numbers of the groups 25, 27, 28 and 29 belonging to amino groups, and 25, 27, 28 and 29 are the numbers of ACNH 2 groups, CH 2 NH 2 groups, CH 3 NH groups and CH 2 NH groups respectively.
9. The method for designing a molecule of impregnating solution according to claim 1, wherein in step S4, the calculation process further includes a step of defining a set, parameters, variables and equations in software.
10. The method of designing a dip molecule according to claim 9, comprising at least one of: The set comprises a set K, a set U and a set P, wherein elements in the set K are groups of the group library, elements in the set U are contribution values of various groups to different properties of molecules, and elements in the set P are types of different groups; The variables include various group types and the number of groups which form the impregnating solution molecule; The equation comprises a constraint equation among the molecular structure and property constraint conditions, a relational expression of the equilibrium adsorption quantity and a relational expression of the formaldehyde removal capability of the modified activated carbon theory.

Description

Design method of environment-friendly active carbon efficient formaldehyde removal modified amine impregnating solution Technical Field The invention belongs to the field of modified activated carbon, and particularly relates to a design method of an environment-friendly efficient formaldehyde-removing modified amine impregnating solution for activated carbon. Background Formaldehyde is the most dominant indoor air pollutant due to its wide sources, simple release conditions, long release period and large harm to human body. Formaldehyde has strong toxicity. Its acute toxicity is generally due to the fact that human body is exposed to air with high formaldehyde concentration, and the formaldehyde is directly contacted with human epidermis to cause eye irritation, lacrimation, dermatitis, cough, etc. However, if formaldehyde enters human blood from respiratory tract for a long time and chronically through inhalation and reacts with nucleic acid, protein and the like to form unstable compounds, the unstable compounds not only can cause chronic respiratory tract diseases, but also can cause toxic symptoms such as headache, dizziness, anxiety and the like. Inhalation of high concentrations of formaldehyde (> 60mg/m 3) can lead to pneumonia and pulmonary oedema, severe and even life threatening. The current indoor formaldehyde purification technology is of a wide variety. Because of the characteristics of economy, high efficiency, simple operation, environmental protection and no secondary pollution, the adsorbent adsorption technology becomes one of the main methods for purifying indoor formaldehyde. When activated carbon is used as an adsorbent for adsorbing formaldehyde, physical adsorption dominates. Physical adsorption is reversible adsorption, and meanwhile, physical adsorption has no selectivity and can not directionally adsorb formaldehyde. At the same time, activated carbon is a nonpolar adsorbent, which limits its ability to adsorb formaldehyde. The surface modification is carried out on the activated carbon, and the adsorption capacity of the activated carbon to formaldehyde is obviously enhanced by introducing some active components to the surface and the internal energy of the pores of the activated carbon. Liquid phase impregnation is an effective and convenient method for achieving activated carbon modification. Specific modifying solvents are selected aiming at target pollutant formaldehyde, and active components in the solvents are loaded on the activated carbon through impregnation, so that the adsorption capacity of the modified activated carbon on formaldehyde is greatly improved compared with that of the original activated carbon. The amine and formaldehyde can undergo condensation reaction to generate methylene amine, so the amine impregnating solution is commonly used for modifying the activated carbon to enhance the formaldehyde removal performance. The traditional activated carbon modified solvent is severely limited in the storage and use process due to the characteristics of irritation, chronic toxicity, inflammability and the like, and the formaldehyde removal capacity of the activated carbon modified by the traditional activated carbon modified solvent still has room for improvement. How to obtain the impregnating solution which can modify the activated carbon to realize efficient formaldehyde removal and meet the production requirements becomes a key research problem. The traditional trial-and-error method for screening the impregnating solution ensures that the production cost is high, the consumed test period is long, and how to reduce the workload, cost and period of test screening is one of the existing main working requirements. Disclosure of Invention Aiming at the problems of large workload of the impregnation liquid test screening for improving the efficiency of removing methanol by the activated carbon, poor effect of the existing impregnation liquid of the modified activated carbon and the like in the research and development of the prior art, the invention provides a design method of the impregnation liquid for efficiently removing formaldehyde by the environment-friendly activated carbon. In order to achieve the above purpose, the method specifically comprises the following technical scheme: in one aspect, the invention provides a method for designing impregnating solution molecules, comprising the following steps: s1, constructing a radical library of a molecular structure of the impregnating solution; s2, constructing a molecular structure and property constraint condition of a impregnating solution molecular structure model; s3, constructing a relational expression of equilibrium adsorption quantity of the impregnating solution molecules adsorbed on the activated carbon, and constructing a relational expression of theoretical formaldehyde removal capacity of the modified activated carbon obtained after modification of the impregnating solution molecules; and S4, adopt