CN115536544A - Compound with demulsification function and preparation method and application thereof - Google Patents
Compound with demulsification function and preparation method and application thereof Download PDFInfo
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- CN115536544A CN115536544A CN202110736068.6A CN202110736068A CN115536544A CN 115536544 A CN115536544 A CN 115536544A CN 202110736068 A CN202110736068 A CN 202110736068A CN 115536544 A CN115536544 A CN 115536544A
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 156
- 238000002360 preparation method Methods 0.000 title abstract description 6
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 119
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 72
- 239000002904 solvent Substances 0.000 claims description 42
- 239000007789 gas Substances 0.000 claims description 39
- 239000011159 matrix material Substances 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 33
- 229910052739 hydrogen Inorganic materials 0.000 claims description 30
- 238000010521 absorption reaction Methods 0.000 claims description 25
- 239000002253 acid Substances 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 6
- 125000000229 (C1-C4)alkoxy group Chemical group 0.000 claims description 4
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 150000001298 alcohols Chemical class 0.000 claims description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 2
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- 150000007522 mineralic acids Chemical class 0.000 claims description 2
- 150000004985 diamines Chemical class 0.000 claims 2
- 239000004291 sulphur dioxide Substances 0.000 claims 1
- 235000010269 sulphur dioxide Nutrition 0.000 claims 1
- 230000002745 absorbent Effects 0.000 abstract description 27
- 239000002250 absorbent Substances 0.000 abstract description 27
- 239000000654 additive Substances 0.000 abstract description 12
- 230000000996 additive effect Effects 0.000 abstract description 12
- 238000005265 energy consumption Methods 0.000 abstract description 8
- 238000000746 purification Methods 0.000 abstract description 8
- 238000000926 separation method Methods 0.000 abstract description 5
- 230000008859 change Effects 0.000 abstract description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 40
- 238000006243 chemical reaction Methods 0.000 description 33
- 239000012071 phase Substances 0.000 description 21
- 230000008929 regeneration Effects 0.000 description 17
- 238000011069 regeneration method Methods 0.000 description 17
- 239000007788 liquid Substances 0.000 description 8
- 150000001412 amines Chemical class 0.000 description 7
- 238000004821 distillation Methods 0.000 description 7
- 239000004721 Polyphenylene oxide Substances 0.000 description 6
- 229920000570 polyether Polymers 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000005261 decarburization Methods 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 230000007704 transition Effects 0.000 description 4
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 238000004128 high performance liquid chromatography Methods 0.000 description 3
- 238000012544 monitoring process Methods 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229940050561 matrix product Drugs 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- ZWRUINPWMLAQRD-UHFFFAOYSA-N nonan-1-ol Chemical compound CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- ZFDIRQKJPRINOQ-HWKANZROSA-N Ethyl crotonate Chemical compound CCOC(=O)\C=C\C ZFDIRQKJPRINOQ-HWKANZROSA-N 0.000 description 1
- 238000006845 Michael addition reaction Methods 0.000 description 1
- WUGQZFFCHPXWKQ-UHFFFAOYSA-N Propanolamine Chemical compound NCCCO WUGQZFFCHPXWKQ-UHFFFAOYSA-N 0.000 description 1
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 description 1
- PBCJIPOGFJYBJE-UHFFFAOYSA-N acetonitrile;hydrate Chemical group O.CC#N PBCJIPOGFJYBJE-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 description 1
- 229940043276 diisopropanolamine Drugs 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- MCVVUJPXSBQTRZ-ONEGZZNKSA-N methyl (e)-but-2-enoate Chemical compound COC(=O)\C=C\C MCVVUJPXSBQTRZ-ONEGZZNKSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- -1 olefin ester Chemical group 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- ZFDIRQKJPRINOQ-UHFFFAOYSA-N transbutenic acid ethyl ester Natural products CCOC(=O)C=CC ZFDIRQKJPRINOQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C243/00—Compounds containing chains of nitrogen atoms singly-bound to each other, e.g. hydrazines, triazanes
- C07C243/10—Hydrazines
- C07C243/12—Hydrazines having nitrogen atoms of hydrazine groups bound to acyclic carbon atoms
- C07C243/14—Hydrazines having nitrogen atoms of hydrazine groups bound to acyclic carbon atoms of a saturated carbon skeleton
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/38—Removing components of undefined structure
- B01D53/40—Acidic components
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/62—Carbon oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/77—Liquid phase processes
- B01D53/78—Liquid phase processes with gas-liquid contact
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/80—Organic bases or salts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/504—Carbon dioxide
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the field of gas separation and purification, and discloses a compound with a demulsification function, and a preparation method and application thereof. The compound has a structure shown in formula (I), wherein A 1 ‑A 4 Each independently of the other is H, -CR 1 R 2 CHR 3 (CH 2 ) n COM、‑CR 1 R 2 CHR 3 (CH 2 ) n CONHN(CR 1 R 2 CHR 3 (CH 2 ) n COM) 2 、‑CR 1 R 2 CHR 3 (CH 2 ) n CONHN(CR 1 R 2 CHR 3 (CH 2 ) n CONHN(CR 1 R 2 CHR 3 (CH 2 ) n COM) 2 ) 2 And CR derived therefrom 1 R 2 CHR 3 (CH 2 ) n The number of CONHN structures is 2 m -1. When the compound is used as an additive, the phase change absorbent is changed from homogeneous phase to heterogeneous phase, and the energy consumption is reduced.
Description
Technical Field
The invention relates to the field of gas separation and purification, in particular to a compound with a demulsification function and a preparation method and application thereof.
Background
The chemical absorption method is one of the most mature methods for gas decarburization at present, but the general problem is high regeneration energy consumption. In response to this problem, work is currently being carried out mainly in the development of new absorbents and in the improvement of processes or in the research of new processes.
Among them, the research idea of new absorbents is mainly to develop new chemical absorbents. In recent years, some researchers have switched thinking ways and started to research the use of phase change absorbents in the decarburization process, so as to solve the problem of high regeneration energy consumption. The literature reports that the process can reduce the liquid amount entering the regeneration tower and further reduce the regeneration energy consumption under the same treatment effect compared with the traditional chemical absorption method.
However, the phase-change absorbent is used for decarburization, and due to the characteristics of large viscosity and surface tension of the absorbent, the separation process of the organic phase and the carrier phase in the rich liquid phase after absorption is slow, and the regeneration process of the subsequent carrier phase and the absorption performance of the lean liquid after regeneration are affected. The chemical demulsifier is added to ensure that the phase change absorbent after decarburization can rapidly and thoroughly realize the transition from homogeneous phase to heterogeneous phase, and reduce the influence of the intermediate transition state on the separation effect of the absorbent, thereby ensuring that the absorbent can be regenerated and absorbed after phase splitting, and improving the gas purification efficiency. Therefore, the development of new demulsifiers has become a focus of attention.
Disclosure of Invention
The invention aims to overcome the technical problems and provides a compound with a demulsification function, a preparation method and application thereof.
In order to achieve the above object, the present invention provides a compound having a demulsification function, the compound having a structure represented by formula (I),
wherein,
A 1 -A 4 each independently is H, -CR 1 R 2 CHR 3 (CH 2 ) n COM、-CR 1 R 2 CHR 3 (CH 2 ) n CONHN(CR 1 R 2 CHR 3 (CH 2 ) n COM) 2 、-CR 1 R 2 CHR 3 (CH 2 ) n CONHN(CR 1 R 2 CHR 3 (CH 2 ) n CONHN(CR 1 R 2 CHR 3 (CH 2 ) n COM) 2 ) 2 And CR derived therefrom 1 R 2 CHR 3 (CH 2 ) n The number of CONHN structures is 2 m -1, m is an integer from 1 to 20;
wherein R is 1 、R 2 And R 3 Each independently is H or C1-C4 alkyl, n is an integer from 0 to 6, M is NHNH 2 Or C1-C4 alkoxy;
wherein, A 1 -A 4 Not all of which are H and A 1 -A 4 At least one of them contains-NHNH 2 。
In a second aspect, the present invention provides a method for preparing a compound having a demulsifying function, the method comprising the steps of:
(1) Reacting hydrazine with CR in the presence of a first solvent 1 R 2 ＝CR 3 (CH 2 ) n COOR 4 Carrying out first contact to obtain a first generation matrix compound; wherein R is 1 、R 2 、R 3 And R 4 Each independently is H or C1-C4 alkyl, and n is an integer of 0-6;
(2) In the presence of a second solvent, carrying out second contact on a first generation matrix compound and hydrazine to obtain a first generation target compound;
(3) Optionally, reacting the first generation target compound with CR in the presence of a third solvent 1 R 2 ＝CR 3 (CH 2 ) n COOR 4 Carrying out third contact to obtain a second generation matrix compound;
(4) Optionally, in the presence of a fourth solvent, carrying out fourth contact on the second generation matrix compound and hydrazine to obtain a second generation target compound;
(5) Optionally, repeating the step (3) and the step (4) according to the rule to obtain a product containing the target compound of the qth generation; wherein q is an integer of 3 to 20.
In a third aspect, the invention provides the use of a compound as described above, a process as described above, or a product containing the target compound as prepared by a process as described above, in gas absorption, in particular in acid gas absorption.
Compared with the prior art, the technical scheme provided by the invention at least has the following advantages:
(1) The invention firstly provides a compound with a demulsification function, which is a compound independently developed by the invention, is prepared from olefine acid ester and hydrazine (hydrazine), and is a novel compound molecule with high Y degree and high order. From the aspect of molecular structure, the compound is similar to a Y-type compound in structure, wherein the Y-type radial growth is continuously repeated outwards from a double-core molecule (hydrazine). When the compound is used as an additive of a gas absorbent (particularly an acid gas absorbent), the absorbent absorbing gas (particularly acid gas) can effectively break the interface property of an organic phase-carrier phase under the action of the additive (the compound provided by the invention), namely break the interface balance, rapidly realize the conversion from homogeneous phase to heterogeneous phase, reduce the influence of an intermediate transition state on the separation effect of the absorbent, further ensure a series of continuous reactions of regeneration and absorption after the phase separation of the absorbent, and improve the gas purification efficiency.
(2) The method for preparing the compound provided by the invention has the advantages of simple steps, high efficiency, environmental friendliness, higher yield and purity, and contribution to industrialization.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a compound with a demulsification function, which has a structure shown in a formula (I),
wherein,
A 1 -A 4 each independently is H, -CR 1 R 2 CHR 3 (CH 2 ) n COM、-CR 1 R 2 CHR 3 (CH 2 ) n CONHN(CR 1 R 2 CHR 3 (CH 2 ) n COM) 2 、-CR 1 R 2 CHR 3 (CH 2 ) n CONHN(CR 1 R 2 CHR 3 (CH 2 ) n CONHN(CR 1 R 2 CHR 3 (CH 2 ) n COM) 2 ) 2 And CR derived therefrom 1 R 2 CHR 3 (CH 2 ) n The number of CONHN structures is 2 m -1, m is an integer from 1 to 20;
wherein R is 1 、R 2 And R 3 Each independently is H or C1-C4 alkyl, n is an integer from 0 to 6, M is NHNH 2 Or C1-C4 alkoxy;
wherein A is 1 -A 4 Not all of which are H and A 1 -A 4 At least one of them containing-NHNH 2 。
In the present invention, the C1-C4 alkyl group includes a C1-C4 linear or branched alkyl group.
In the present invention, the C1-C4 alkoxy group includes a C1-C4 linear or branched alkoxy group.
According to some embodiments of the invention, A 1 -A 4 Each independently is-CR 1 R 2 CHR 3 (CH 2 ) n COM or-CR 1 R 2 CHR 3 (CH 2 ) n CONHN(CR 1 R 2 CHR 3 (CH 2 ) n COM) 2 、-CR 1 R 2 CHR 3 (CH 2 ) n CONHN(CR 1 R 2 CHR 3 (CH 2 ) n CONHN(CR 1 R 2 CHR 3 (CH 2 ) n COM) 2 ) 2 And CR derived therefrom 1 R 2 CHR 3 (CH 2 ) n CONHN is one of m groups, and m is an integer of 1-10.
According to some embodiments of the invention, R 1 、R 2 And R 3 Each independently is one of H, methyl and ethyl.
According to some embodiments of the invention, n is an integer from 0 to 4.
According to some embodiments of the invention, m ≦ 5.
According to some embodiments of the invention, M is NHNH 2 。
According to some embodiments of the invention, A 1 -A 4 Is the same and is-CR 1 R 2 CHR 3 (CH 2 ) n COM of which R 1 ＝H，R 2 ＝H，R 3 = H, n is 0, M is NHNH 2 (ii) a Or,
A 1 -A 4 are identical and are-CR 1 R 2 CHR 3 (CH 2 ) n COM, wherein R 1 ＝H，R 2 ＝H，R 3 = H, n is 1, M is NHNH 2 (ii) a Or,
A 1 -A 4 is the same and is-CR 1 R 2 CHR 3 (CH 2 ) n COM of which R 1 ＝Me，R 2 ＝H，R 3 = H, n is 0, M is NHNH 2 (ii) a Or,
A 1 -A 4 are identical and are CR 1 R 2 CHR 3 (CH 2 ) n The number of CONHN structures is 2 m A group of-1, wherein R 1 ＝H，R 2 ＝H，R 3 = H, n is 0, m is 1, M is NHNH 2 (ii) a Or,
A 1 -A 4 are identical and are CR 1 R 2 CHR 3 (CH 2 ) n The number of CONHN structures is 2 m A group of-1, wherein R 1 ＝H，R 2 ＝H，R 3 = H, n is 1, m is 1, M is NHNH 2 (ii) a Or,
A 1 -A 4 are identical and are CR 1 R 2 CHR 3 (CH 2 ) n The number of CONHN structures is 2 m A group of-1, wherein R 1 ＝Me，R 2 ＝H，R 3 = H, n is 0, m is 1, M is NHNH 2 (ii) a Or,
A 1 -A 4 are identical and are CR 1 R 2 CHR 3 (CH 2 ) n The number of CONHN structures is 2 m A group of-1, wherein R 1 ＝H，R 2 ＝H，R 3 = H, n is 0, m is 2, M is NHNH 2 (ii) a Or,
A 1 -A 4 are identical and are CR 1 R 2 CHR 3 (CH 2 ) n The number of CONHN structures is 2 m A group of-1, wherein R 1 ＝H，R 2 ＝H，R 3 = H, n is 1, m is 2, M is NHNH 2 (ii) a Or,
A 1 -A 4 are identical and are CR 1 R 2 CHR 3 (CH 2 ) n The number of CONHN structures is 2 m A group of-1, wherein R 1 ＝Me，R 2 ＝H，R 3 = H, n is 0, m is 2, M is NHNH 2 (ii) a Or,
A 1 -A 4 are identical and are CR 1 R 2 CHR 3 (CH 2 ) n The number of CONHN structures is 2 m A group of-1, wherein R 1 ＝H，R 2 ＝H，R 3 = H, n is 0, m is 3, M is NHNH 2 (ii) a Or,
A 1 -A 4 are identical and are CR 1 R 2 CHR 3 (CH 2 ) n The number of CONHN structures is 2 m A group of-1, wherein R 1 ＝H，R 2 ＝H，R 3 = H, n is 1, m is 3, M is NHNH 2 (ii) a Or,
A 1 -A 4 are identical and are CR 1 R 2 CHR 3 (CH 2 ) n The number of CONHN structures is 2 m A group of-1, wherein R 1 ＝Me，R 2 ＝H，R 3 = H, n is 0, m is 3, M is NHNH 2 (ii) a Or,
A 1 -A 4 are identical and are CR 1 R 2 CHR 3 (CH 2 ) n The number of CONHN structures is 2 m A group of-1, wherein R 1 ＝H，R 2 ＝H，R 3 = H, n is 0, m is 4, M is NHNH 2 (ii) a Or,
A 1 -A 4 are identical and are CR 1 R 2 CHR 3 (CH 2 ) n The number of CONHN structures is 2 m A group of-1, wherein R 1 ＝H，R 2 ＝H，R 3 = H, n is 1, m is 4, M is NHNH 2 (ii) a Or,
A 1 -A 4 are identical and are CR 1 R 2 CHR 3 (CH 2 ) n The number of CONHN structures is 2 m A group of-1, wherein R 1 ＝Me，R 2 ＝H，R 3 = H, n is 0, m is 4, M is NHNH 2 。
The inventor of the present invention has found that based on the michael addition reaction principle, grafting groups (such as an olefin ester chain) with different lengths can react with hydrazine (as an initiating core), and the compound can continuously and repeatedly grow radially outwards to obtain compounds containing different or same substituted grafting groups, and the compounds can be well used in gas absorption. However, from the viewpoint of cost and ease of handling, it is preferable to graft a molecule similar to the Y-type compound with the same graft group to obtain high symmetry.
Accordingly, in a second aspect, the present invention provides a method for preparing a compound having a demulsifying function, the method comprising the steps of:
(1) Reacting hydrazine with CR in the presence of a first solvent 1 R 2 ＝CR 3 (CH 2 ) n COOR 4 Performing a first contact to obtain a first-generation matrix compound (1G matrix compound); wherein R is 1 、R 2 、R 3 And R 4 Each independently is H or C1-C4 alkyl, and n is an integer of 0-6;
(2) Second contacting the first-generation base compound with hydrazine in the presence of a second solvent to obtain a first-generation target compound (1G target compound);
(3) Optionally, reacting the first generation target compound with CR in the presence of a third solvent 1 R 2 ＝CR 3 (CH 2 ) n COOR 4 Carrying out a third contact to obtain a second generation matrix compound (2G matrix compound);
(4) Optionally, fourth contacting the second generation base compound with hydrazine in the presence of a fourth solvent to yield a second generation target compound (2G target compound);
(5) Optionally, repeating the step (3) and the step (4) according to the rule to obtain a product containing the q generation target compound; wherein q is an integer of 3 to 20.
According to some embodiments of the invention, R 1 、R 2 、R 3 And R 4 Each independently is one of H, methyl and ethyl.
According to some embodiments of the invention, n is an integer from 0 to 4.
According to some embodiments of the present invention, in step (1), the first solvent may be selected from water and/or C1-C4 alcohols, preferably methanol and/or water.
According to some embodiments of the present invention, the first solvent may be used in an amount of 2 to 20mL, preferably 3 to 15mL, relative to 1g of hydrazine.
According to some embodiments of the invention, in step (1), in order to make the reaction proceed better, CR is used 1 R 2 ＝CR 3 (CH 2 ) n COOR 4 With the amount of hydrazine there is a requirement and preferably CR 1 R 2 ＝CR 3 (CH 2 ) n COOR 4 Excess, e.g. CR 1 R 2 ＝CR 3 (CH 2 ) n COOR 4 The molar ratio to hydrazine may be (4-12): 1, preferably (6-10): 1.
according to some embodiments of the invention, the first contacting is by: adding hydrazine and/or hydrazine solution into CR at 20-40 deg.C 1 R 2 ＝CR 3 (CH 2 ) n COOR 4 In solution.
In the invention, in the step (1), the hydrazine solution is obtained by dissolving hydrazine in the first solvent; the CR 1 R 2 ＝CR 3 (CH 2 ) n COOR 4 Solution is formed by CR 1 R 2 ＝CR 3 (CH 2 ) n COOR 4 Dissolving in the first solvent to obtain; the amount of the first solvent used for dissolution is not particularly limited, as long as the requirements of the present invention can be satisfied.
According to some embodiments of the present invention, in order to obtain better effect, there is a certain requirement for the adding speed of the hydrazine and/or the hydrazine solution in step (1), preferably, the adding speed is 1-10mL/min, more preferably 1-5mL/min, relative to 100mL of the hydrazine and/or the hydrazine solution.
According to some embodiments of the present invention, the time of the first contacting may be 12 to 72 hours, preferably 24 to 48 hours. Wherein, when the hydrazine and/or hydrazine solution begins to drop, the hydrazine is mixed with CR 1 R 2 ＝CR 3 (CH 2 ) n COOR 4 The reaction starts.
According to some embodiments of the present invention, in the step (2), the second solvent may be selected from water and/or C1-C4 alcohol, preferably methanol and/or water.
According to some embodiments of the present invention, the amount of the second solvent may be 2 to 20mL, preferably 3 to 15mL, relative to 1g of hydrazine.
According to some embodiments of the present invention, in step (2), there is a certain requirement for the amount of the first generation base compound and hydrazine to be used in order to make the reaction proceed better, and preferably, the first generation base compound is in excess, for example, the molar ratio of hydrazine to the first generation base compound may be (4-20): 1, preferably (8-16): 1.
according to some embodiments of the invention, the second contacting is by: the solution of the first generation matrix compound is added to the hydrazine and/or hydrazine solution at 20-40 c.
In the invention, in the step (2), the hydrazine solution is obtained by dissolving hydrazine in the second solvent; the solution of the first-generation base compound is obtained by dissolving the first-generation base compound in the second solvent; the amount of the second solvent for dissolution is not particularly limited, as long as the requirements of the present invention can be satisfied.
According to some embodiments of the present invention, in step (2), in order to make the reaction proceed better, there is a certain requirement for the addition rate of the first-generation base compound solution, preferably, the addition rate is 1 to 20mL/min, more preferably 1 to 10mL/min, relative to 100mL of the first-generation base compound solution.
According to some embodiments of the present invention, the second contacting time may be 12 to 72 hours, preferably 24 to 48 hours. Wherein the first-generation base compound and hydrazine begin to react when the solution of the first-generation base compound begins to drip.
According to some embodiments of the invention, in step (3), in order to allow the reaction to proceed better, the first generation of the target compound is reacted with CR 1 R 2 ＝CR 3 (CH 2 ) n COOR 4 The amount of (A) is subject to certain requirements and preferably CR 1 R 2 ＝CR 3 (CH 2 ) n COOR 4 In excess, e.g. of the first generation target compound with CR 1 R 2 ＝CR 3 (CH 2 ) n COOR 4 May be 1: (8-20), preferably 1: (12-18).
According to some embodiments of the invention, the third contacting is by: adding a solution of the first generation target compound to the CR at 20-40 deg.C 1 R 2 ＝CR 3 (CH 2 ) n COOR 4 In solution.
In the present invention, in the step (3), the solution of the first-generation target compound is obtained by dissolving the first-generation target compound in the third solvent; the CR 1 R 2 ＝CR 3 (CH 2 ) n COOR 4 Solution is formed by CR 1 R 2 ＝CR 3 (CH 2 ) n COOR 4 Dissolving in the third solvent to obtain; the amount of the third solvent for dissolution is not particularly limited, as long as the requirements of the present invention can be satisfied.
According to some embodiments of the present invention, there is a requirement for the rate of addition of the solution of the first generation target compound in order to allow the reaction to proceed better, preferably at a rate of 1-20mL/min, more preferably 1-10mL/min, relative to 100mL of the solution of the first generation target compound.
According to some embodiments of the invention, the third contact time is between 12 and 72h, preferably between 24 and 48h. Wherein the first-generation target compound is mixed with CR when the solution of the first-generation target compound starts to drop 1 R 2 ＝CR 3 (CH 2 ) n COOR 4 The reaction starts.
According to some embodiments of the invention, the third solvent is used in an amount of 2-20mL, preferably 3-15mL, relative to 1g of the first generation target compound.
According to some embodiments of the present invention, there is a requirement in step (4) for the amount of the second generation base compound and the hydrazine to be used, and preferably, the hydrazine is in excess, and the molar ratio of the second generation base compound to the hydrazine is 1: (16-32), preferably 1: (18-24).
According to some embodiments of the invention, the fourth contacting is by: the fourth contact mode is as follows: the solution of the second generation base compound is added to the hydrazine and/or hydrazine solution at 20-40 c.
In the invention, in the step (4), the hydrazine solution is obtained by dissolving hydrazine in the fourth solvent; the solution of the second generation matrix compound is obtained by dissolving the second generation matrix compound in the fourth solvent; the amount of the fourth solvent for dissolution is not particularly limited, as long as the requirements of the present invention can be satisfied.
According to some embodiments of the present invention, the fourth contact time may be 12 to 72 hours, preferably 24 to 48 hours. Wherein the second generation matrix compound begins to react with the hydrazine when the solution of the second generation matrix compound begins to drop.
According to some embodiments of the present invention, the fourth solvent may be used in an amount of 2 to 20mL, preferably 3 to 15mL, relative to 1g of hydrazine.
According to some embodiments of the present invention, in step (4), there is a requirement for the rate of addition of the solution of the second-generation base compound in order to allow the reaction to proceed better, preferably, the rate of addition is 1 to 20mL/min, more preferably 1 to 10mL/min, relative to 100mL of the solution of the second-generation base compound.
In the present invention, in the step (5), the ratio of the amounts of the respective substances and the time of contact in the process of repeating the steps (3) and (4) are not particularly limited as long as the requirements of the present invention can be satisfied.
In the present invention, the steps (1) and (3) are preferably carried out in the presence of a polymerization inhibitor selected from hydroquinone monomethyl ether and/or hydroquinone monomethyl ether. Wherein the addition amount of the polymerization inhibitor accounts for CR 1 R 2 ＝CR 3 (CH 2 ) n COOR 4 0.1-1wt%.
In the present invention, it is preferable that the method further comprises a purification step, for example, in the step (1), the reaction solution after the first contact is subjected to a first post-treatment (purification treatment). The step of the first post-treatment is not particularly limited as long as the requirements of the present invention can be satisfied, and may be performed, for example, by: distilling the reaction solution after the first contact under reduced pressure at 30-50 deg.C and vacuum degree of 50-70kPa for 10-20h.
In the present invention, it is preferable that the step (2) further comprises subjecting the reaction solution after the second contact to a second post-treatment (purification treatment). The step of the second post-treatment is not particularly limited as long as the requirements of the present invention can be satisfied, and may be performed, for example, by: distilling the reaction solution after the second contact under reduced pressure at 40-80 deg.C and vacuum degree of 60-90kPa for 10-30h.
Similarly, the step (3), the step (4) and the step (5) can be separated and purified with reference to the purification step in the aforementioned step (1) or step (2). In the present invention, the obtained product containing the q-th generation target compound can be directly used as an additive (demulsifier), or can be used as an additive (demulsifier) after a simple solvent removal step (such as distillation).
In the present invention, the first solvent, the second solvent, the third solvent and the fourth solvent may be the same or different, as long as the first contact, the second contact, the third contact and the fourth contact are provided with a medium to promote the addition reaction or the reaction of the amine group and the ester group.
In the present invention, the aforementioned compounds are useful as demulsifiers in acid gas absorption. Accordingly, in the present invention, there is also provided a composition for acid gas absorption comprising an absorbent and an additive; wherein the absorbent comprises at least one of organic amine, polyether and C7-C10 fatty alcohol.
In the invention, the weight ratio of the absorbent to the additive is 100: (0.1-10), preferably 100: (0.5-5).
In the invention, the absorbent is selected from organic amine and polyether.
In the invention, based on the total weight of the absorbent and the additive in the composition, the content of the organic amine is 1-50wt%, the content of the polyether is 40-99wt%, and the content of the additive is 0.005-10wt%.
In the invention, based on the total weight of the absorbent and the additive in the composition, the content of the organic amine is 5-50wt%, the content of the polyether is 45-95wt%, and the content of the additive is 0.01-5wt%.
In the invention, the organic amine is C1-C6 alcohol amine, and is selected from at least one of monoethanolamine, diethanolamine, triethanolamine, 3-propanolamine, monoisopropanolamine, diisopropanolamine and triisopropanolamine, preferably from at least one of monoethanolamine, diethanolamine and triethanolamine.
In the present invention, the polyether has a weight average molecular weight of 200 to 600, preferably 250 to 270; selected from dimethyl ether of polyethylene glycol and/or monomethyl ether of polyethylene glycol.
Among them, the C7-C10 aliphatic alcohol may be, for example, n-heptanol, n-octanol, nonanol or decanol.
In a third aspect, the invention provides an application of the compound, the method and the compound with a demulsification function prepared by the method in gas absorption, in particular an application in acid gas absorption, wherein the compound comprises a target compound (including at least one of a first generation target compound, a second generation target compound, \8230;, a q generation target compound).
According to some embodiments of the invention, the acid gas is an inorganic acid gas, preferably at least one selected from the group consisting of carbon dioxide, sulfur dioxide and hydrogen sulfide.
In the present invention, the parameter measured during regeneration is the acid gas value in the carrier phase, i.e. the absorption of CO in the carrier phase 2 Relative content (V) CO2 /V Solutions of ，mL/mL)。
The present invention will be described in detail below by way of examples.
In the following examples, the raw materials are all commercially available products unless otherwise specified.
Monitoring the progress of the reaction by HPLC; yield = conversion x selectivity;
conversion = the percentage of the amount of reactants participating in the reaction (the reacted amount of starting materials) to the amount entering the reactor (the starting amount of starting materials);
selectivity = amount of key component (mol) consumed to produce the target product/amount of key component (mol) participating in the reaction; the purity is detected by HPLC;
analytical conditions for HPLC: the chromatographic column is a Phenomenex C18 column (250 mm multiplied by 4.6mm,4 mu m); the mobile phase is acetonitrile-water (volume ratio is 70.
Example 1
1G base compound:
1G target compound:
(1) In a three-necked flask, 344.36g of Methyl Acrylate (MA) was dissolved in 100mL of methanol, and 3.5g of hydroquinone monomethyl ether was added to obtain a methanol solution of methyl acrylate (MA solution); then 16.02g of hydrazine (AH) was dissolved in 50mL of methanol to obtain a methanol solution of hydrazine (AH solution), and the AH solution was placed in a constant pressure dropping funnel; slowly dropwise adding AH solution into the MA solution under stirring at 25 ℃, and finishing dropwise adding for 0.5h, wherein the weight ratio of MA: the molar ratio of AH to AH is 8; after the reaction is monitored to be complete, the product after the reaction is subjected to reduced pressure distillation at 35 ℃ and the vacuum degree of 60kPa for 16h, methanol and excessive MA are removed, and the obtained light yellow product is the 1G matrix compound, the purity is 98.5wt%, and the yield is 93.9%.
(2) Dissolving the 1G matrix product obtained in the step (1) in 100mL of methanol, placing the solution into a constant-pressure dropping funnel after the 1G matrix compound is completely dissolved to obtain a methanol solution of the 1G matrix compound, and adding excessive AH into a three-mouth reaction bottle so that the molar ratio of the AH to the 1G matrix compound is 16:1; slowly dripping 1G methanol solution of the matrix compound under stirring at 25 ℃, keeping the temperature for 24 hours after 0.5 hour of dripping is finished, monitoring the reaction to be complete, carrying out reduced pressure distillation on the product after the reaction for 16 hours at 55 ℃ and under the vacuum degree of 80kPa, removing methanol and excessive AH, and finally increasing the viscosity in a distillation flask to obtain a nearly light yellow viscous liquid, namely the 1G target compound, wherein the purity is 95.2wt%, and the yield is 87.1%.
Example 2
2G base compound:
2G target Compound:
repeating the steps (1) and (2) in the preparation example 1 to obtain a 1G matrix compound and a 1G target compound respectively;
(3) In the same manner as in step (1), 137.74g of Methyl Acrylate (MA) was dissolved in 100mL of methanol in a three-necked flask, and 0.2g of hydroquinone monomethyl ether was added to give a methanol solution of methyl acrylate (MA solution); then 37.6G of the 1G target compound is dissolved in 50mL of methanol to obtain a methanol solution of the 1G target compound, and the methanol solution is placed in a constant pressure dropping funnel; slowly dropwise adding a 1G methanol solution of a target compound into the MA solution under stirring at 25 ℃, finishing dropwise adding after 0.5h, wherein the molar ratio of MA to the 1G target compound is 16; after the reaction is monitored to be complete, the product after the reaction is subjected to reduced pressure distillation at 35 ℃ and the vacuum degree of 60kPa for 16h, methanol and excessive MA are removed, and the obtained light yellow product is the 2G matrix compound, the purity is 98.3wt%, and the yield is 80.0%.
(4) Dissolving the 2G matrix product obtained in the step (3) in 100mL of methanol, placing the solution into a constant-pressure dropping funnel after the 2G matrix compound is completely dissolved to obtain a methanol solution of the 2G matrix compound, and adding excessive AH into a three-mouth reaction bottle so that the molar ratio of the AH to the 2G matrix compound is 16:1; slowly dripping a methanol solution of the 2G matrix compound under stirring at 25 ℃, keeping the temperature for 24 hours after 1 hour of dripping is finished, monitoring the reaction to be complete, carrying out reduced pressure distillation on the product after the reaction for 16 hours at 55 ℃ and under the vacuum degree of 80kPa, removing methanol and excessive AH, and finally increasing the viscosity in a distillation flask to obtain a light yellow viscous liquid, namely the 2G target compound, wherein the purity is 93.6wt%, and the yield is 71.3%.
Example 3
3G base compound:
3G target compound:
the 3G base compound and the 3G target compound were prepared by repeating steps (3) and (4) using the 2G target compound as a reactant in the manner of example 2.
Wherein, the purity of the 3G matrix compound is 97.6wt percent, and the yield is 65.7 percent; the purity of the 3G title compound was 93.2wt% with a yield of 55.8%.
Example 4
The 4G base compound and the 4G target compound were prepared by repeating steps (3) and (4) using the 3G target compound as a reactant in the manner of example 3.
Wherein, the purity of the 4G matrix compound is 97.2 weight percent, and the yield is 49.1 percent; the 4G target compound, with a purity of 92.8wt% and a yield of 42.3%.
Example 5
The 5G base compound and the 5G target compound were prepared by repeating steps (3) and (4) using the 2G target compound as a reactant in the manner of example 4.
Wherein, the purity of the 5G matrix compound is 96.3wt percent, and the yield is 37.2 percent; the purity of the 5G title compound was 92.2wt% with a yield of 32.7%.
Example 6
The procedure is as in example 2, except that 344.36g of Methyl Acrylate (MA) are replaced by 400.48g of ethyl acrylate.
Finally, the 1G base compound, having a purity of 98.4wt% and a yield of 92.5%; the purity of the 1G title compound was 95.8wt% with a yield of 84.6%.
Example 7
The procedure is as in example 2, except that 344.36g of Methyl Acrylate (MA) are replaced by 400.44g of methyl crotonate.
Finally, 1G base compound, purity 98.2wt%, yield 93.3%; the purity of the 1G target compound was 94.2wt%, and the yield was 85.8%.
Example 8
The procedure is as in example 2, except that 456.56g of ethyl crotonate are used instead of 344.36g of Methyl Acrylate (MA).
Finally, the 1G base compound, having a purity of 98.8wt% and a yield of 91.4%; the purity of the 1G title compound was 93.2wt% with a yield of 82.3%.
The following test examples are provided to illustrate the use of the compounds prepared in the above examples for acid gas absorption
Organic amine, polyether and additive are prepared into a composition formula according to the content shown in table 1, and an acid gas absorbent (water is used as a solvent) of the organic amine with the molar concentration of 3mol/L is prepared. Wherein the weight average molecular weight of the polyethylene glycol dimethyl ether used is 260; polyoxyethylene polyoxypropylene stearyl ether was purchased from Daqing Renwei chemical Co.
Gas absorption experiment: raw material gas (acid gas CO) 2 12.8 percent of volume concentration) is put into an absorption tube filled with absorbent at 40 +/-0.5 ℃ after passing through a moisture absorption bottle and a buffer bottle, wherein the gas flow of the raw material gas is controlled to be 100mL/min, the bubbling absorption is carried out, the absorption temperature is controlled by a constant temperature tank, and after a period of time, the CO in the vented tail gas is treated 2 The content is monitored and analyzed by a flue gas analyzer, then a gas source is closed, and a carrier phase absorbing acid gas is taken for liquid phase analysis. Wherein, a raw gas pipeline is reserved to adjust the content of acid gas in the raw gas. Wherein the CO absorbed in the absorbent is treated by a gas generation method 2 Analyzing, specifically, putting a certain amount of sample into a neutralization reaction bottle, putting excessive dilute sulfuric acid solution into a straight tube in the reaction bottle, covering a stopper tightly, and recording a reading V when the liquid level of the solution bottle is level with the liquid level of the straight tube with scales o . The liquid in the reaction bottle is contacted and reacted with CO 2 Separating out, recording the reading V when the two liquid levels are equal 1 。V 1 And V o The difference is the CO generated after the reaction 2 Volume from which the CO in solution can be back-calculated 2 And (4) content.
Regeneration experiments: and (4) finishing the absorption reaction according to the absorption reaction time of 6h, and taking the carrier phase for a regeneration test. Wherein the regeneration temperature is controlled to be 110 ℃, and the rotation speed of mechanical stirring is 150rpm, 1000W and 30min after heating, and measuring CO in the solution 2 Content to determine desorbed CO 2 The amount of (c).
The results of the gas absorption test and the regeneration test in the above test examples and comparative test examples are shown in Table 2.
TABLE 1
TABLE 2
In table 2, t1 represents "time for which carrier phase droplet sedimentation occurs for the first time after aeration", and a smaller t1 indicates a stronger phase transition capability of the absorbent, i.e., a higher tendency to occur; t2 represents the time for completely separating the carrier phase from the organic phase to stand after the absorption reaction is finished, and the smaller t2 is, the better the effect of the phase change process of the absorbent is, and the reduction of the regeneration energy consumption of the absorbent is facilitated;
the energy consumption for regeneration means "per unit volume of CO regenerated 2 The energy consumption "required to be consumed is calculated by the following formula: regenerative energy consumption =1 × 30 × 60/(L) 0 -L 30 ) The unit kJ/mL; wherein L is 0 Represents the initial acid gas value (regeneration time 0 min) in the carrier phase in the regeneration process; l is 30 The acid gas value at 30min in the carrier phase during regeneration is shown.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including various technical features being combined in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (11)
1. A compound with a demulsification function is characterized in that the compound has a structure shown in a formula (I),
wherein,
A 1 -A 4 each independently of the other is H, -CR 1 R 2 CHR 3 (CH 2 ) n COM、-CR 1 R 2 CHR 3 (CH 2 ) n CONHN(CR 1 R 2 CHR 3 (CH 2 ) n COM) 2 、-CR 1 R 2 CHR 3 (CH 2 ) n CONHN(CR 1 R 2 CHR 3 (CH 2 ) n CONHN(CR 1 R 2 CHR 3 (CH 2 ) n COM) 2 ) 2 And CR derived therefrom 1 R 2 CHR 3 (CH 2 ) n The number of CONHN structures is 2 m -1, m is an integer from 1 to 20;
wherein R is 1 、R 2 And R 3 Each independently is H or C1-C4 alkyl, n is an integer from 0 to 6, M is NHNH 2 Or C1-C4 alkoxy;
wherein, A 1 -A 4 Not all of which are H and A 1 -A 4 At least one of them containing-NHNH 2 。
2. The compound of claim 1, wherein a 1 -A 4 Each independently is-CR 1 R 2 CHR 3 (CH 2 ) n COM or-CR 1 R 2 CHR 3 (CH 2 ) n CONHN(CR 1 R 2 CHR 3 (CH 2 ) n COM) 2 、-CR 1 R 2 CHR 3 (CH 2 ) n CONHN(CR 1 R 2 CHR 3 (CH 2 ) n CONHN(CR 1 R 2 CHR 3 (CH 2 ) n COM) 2 ) 2 And CR derived therefrom 1 R 2 CHR 3 (CH 2 ) n The number of CONHN structures is 2 m -1, m is an integer from 1 to 10.
3. A compound according to claim 1 or 2, wherein R 1 、R 2 And R 3 Each independently is one of H, methyl and ethyl;
and/or n is an integer from 0 to 4;
and/or m is less than or equal to 5;
and/or, M is NHNH 2 。
4. A compound according to any one of claims 1 to 3, wherein a 1 -A 4 Is the same and is-CR 1 R 2 CHR 3 (CH 2 ) n COM, wherein R 1 ＝H，R 2 ＝H，R 3 = H, n is 0, M is NHNH 2 (ii) a Or,
A 1 -A 4 is the same and is-CR 1 R 2 CHR 3 (CH 2 ) n COM of which R 1 ＝H，R 2 ＝H，R 3 = H, n is 1, M is NHNH 2 (ii) a Or,
A 1 -A 4 is the same and is-CR 1 R 2 CHR 3 (CH 2 ) n COM, wherein R 1 ＝Me，R 2 ＝H，R 3 = H, n is 0, M is NHNH 2 (ii) a Or,
A 1 -A 4 are identical and are CR 1 R 2 CHR 3 (CH 2 ) n The number of CONHN structures is 2 m A group of-1, wherein R 1 ＝H，R 2 ＝H，R 3 = H, n is 0, m is 1, M is NHNH 2 (ii) a Or,
A 1 -A 4 are identical and are CR 1 R 2 CHR 3 (CH 2 ) n The number of CONHN structures is 2 m A group of-1, wherein R 1 ＝H，R 2 ＝H，R 3 = H, n is 1, m is 1, M is NHNH 2 (ii) a Or,
A 1 -A 4 are identical and are CR 1 R 2 CHR 3 (CH 2 ) n The number of CONHN structures is 2 m A group of-1, wherein R 1 ＝Me，R 2 ＝H，R 3 = H, n is 0, m is 1, M is NHNH 2 (ii) a Or,
A 1 -A 4 are identical and are CR 1 R 2 CHR 3 (CH 2 ) n The number of CONHN structures is 2 m A group of-1, wherein R 1 ＝H，R 2 ＝H，R 3 = H, n is 0, m is 2, M is NHNH 2 (ii) a Or,
A 1 -A 4 are identical and are CR 1 R 2 CHR 3 (CH 2 ) n The number of CONHN structures is 2 m A group of-1, wherein R 1 ＝H，R 2 ＝H，R 3 = H, n is 1, m is 2, M is NHNH 2 (ii) a Or,
A 1 -A 4 are identical and are CR 1 R 2 CHR 3 (CH 2 ) n The number of CONHN structures is 2 m A group of-1, wherein R 1 ＝Me，R 2 ＝H，R 3 = H, n is 0, m is 2, M is NHNH 2 (ii) a Or,
A 1 -A 4 are identical and are CR 1 R 2 CHR 3 (CH 2 ) n The number of CONHN structures is 2 m A group of-1, wherein R 1 ＝H，R 2 ＝H，R 3 = H, n is 0, m is 3, M is NHNH 2 (ii) a Or,
A 1 -A 4 are identical and are CR 1 R 2 CHR 3 (CH 2 ) n The number of CONHN structures is 2 m A group of-1, wherein R 1 ＝H，R 2 ＝H，R 3 = H, n is 1, m is 3, M is NHNH 2 (ii) a Or,
A 1 -A 4 are identical and are CR 1 R 2 CHR 3 (CH 2 ) n The number of CONHN structures is 2 m A group of-1, wherein R 1 ＝Me，R 2 ＝H，R 3 = H, n is 0, m is 3, M is NHNH 2 (ii) a Or,
A 1 -A 4 are identical and are CR 1 R 2 CHR 3 (CH 2 ) n The number of CONHN structures is 2 m A group of-1, wherein R 1 ＝H，R 2 ＝H，R 3 = H, n is 0, m is 4, M is NHNH 2 (ii) a Or,
A 1 -A 4 are identical and are CR 1 R 2 CHR 3 (CH 2 ) n The number of CONHN structures is 2 m A group of-1, wherein R 1 ＝H，R 2 ＝H，R 3 = H, n is 1, m is 4, M is NHNH 2 (ii) a Or,
A 1 -A 4 are identical and are CR 1 R 2 CHR 3 (CH 2 ) n The number of CONHN structures is 2 m A group of-1, wherein R 1 ＝Me，R 2 ＝H，R 3 = H, n is 0, m is 4, M is NHNH 2 。
5. A method for preparing a compound having a demulsifying function, the method comprising the steps of:
(1) Reacting hydrazine with CR in the presence of a first solvent 1 R 2 ＝CR 3 (CH 2 ) n COOR 4 Performing a first contact to obtain a product containing a first-generation matrix compound; wherein R is 1 、R 2 、R 3 And R 4 Each independently is H or C1-C4 alkyl, and n is an integer of 0-6;
(2) In the presence of a second solvent, carrying out second contact on the product containing the first generation matrix compound and hydrazine to obtain a product containing a first generation target compound;
(3) Optionally, the product containing the first generation target compound is contacted with CR in the presence of a third solvent 1 R 2 ＝CR 3 (CH 2 ) n COOR 4 Carrying out a third contact to obtain a product containing a second generation matrix compound;
(4) Optionally, in the presence of a fourth solvent, carrying out fourth contact on the product containing the second generation matrix compound and hydrazine to obtain a product containing a second generation target compound;
(5) Optionally, repeating the step (3) and the step (4) according to the rule to obtain a product containing the target compound of the qth generation; wherein q is an integer of 3 to 20.
6. The method of claim 5, wherein R 1 、R 2 、R 3 And R 4 Each independently is one of H, methyl and ethyl, and/or n is an integer from 0 to 4.
7. The process according to claim 5 or 6, wherein in step (1), the first solvent is selected from water and/or C1-C4 alcohols, preferably methanol and/or water;
and/or, the amount of the first solvent is 2-20mL, preferably 3-15mL, relative to 1g of hydrazine;
and/or, CR 1 R 2 ＝CR 3 (CH 2 ) n COOR 4 The molar ratio of the diamine to the diamine is (4-12): 1, preferably (6-10): 1;
and/or the first contact mode is as follows: adding hydrazine and/or hydrazine solution into CR at 20-40 deg.C 1 R 2 ＝CR 3 (CH 2 ) n COOR 4 In solution;
preferably, the adding speed is 1-10mL/min, more preferably 1-5mL/min, relative to 100mL of hydrazine and/or hydrazine solution;
and/or the first contact time is 12-72h, preferably 24-48h.
8. The process according to any one of claims 5 to 7, wherein in step (2), the second solvent is selected from water and/or C1-C4 alcohols, preferably methanol and/or water;
and/or, the amount of the second solvent is 2-20mL, preferably 3-15mL, relative to 1g of hydrazine;
and/or the molar ratio of hydrazine to the first generation matrix compound is (4-20): 1, preferably (8-16): 1;
and/or the second contact mode is as follows: adding a solution of a first generation matrix compound to the hydrazine and/or hydrazine solution at 20-40 ℃;
preferably, the addition rate is 1-20mL/min, more preferably 1-10mL/min, relative to 100mL of the solution of the first-generation base compound;
preferably, the second contact time is 12-72h, preferably 24-48h.
9. The method of any one of claims 5-8, wherein in step (3), the first generation target compound is reacted with CR 1 R 2 ＝CR 3 (CH 2 ) n COOR 4 In a molar ratio of 1: (8-20), preferably 1: (12-18);
and/or the third contact mode is as follows: adding a solution of the first generation target compound to the CR at 20-40 deg.C 1 R 2 ＝CR 3 (CH 2 ) n COOR 4 In solution;
preferably, the addition rate is 1-20mL/min, more preferably 1-10mL/min, relative to 100mL of the solution of the first generation target compound;
and/or the time of the third contact is 12 to 72 hours, preferably 24 to 48 hours;
and/or, the amount of the third solvent is 2-20mL, preferably 3-15mL, relative to 1g of the first generation target compound;
and/or, in the step (4), the molar ratio of the second generation base compound to hydrazine is 1: (16-32), preferably 1: (18-24);
and/or, the fourth contact mode is as follows: the second contact mode is as follows: adding the solution of the second generation base compound into hydrazine and/or a hydrazine solution at 20-40 ℃;
and/or the fourth contact time is 12-72h, preferably 24-48h; and/or, the amount of the fourth solvent is 2-20mL, preferably 3-15mL, relative to 1g of hydrazine;
preferably, the rate of addition is 1-20mL/min, more preferably 1-10mL/min, relative to 100mL of the solution of the second-generation matrix compound.
10. Use of a compound according to any one of claims 1 to 4, a process according to any one of claims 5 to 9 and a product containing a target compound prepared by a process according to any one of claims 5 to 9 in gas absorption, in particular in acid gas absorption.
11. Use according to claim 10, wherein the acid gas is an inorganic acid gas, preferably at least one selected from carbon dioxide, sulphur dioxide and hydrogen sulphide.
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