CN115536544B - 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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- CN115536544B CN115536544B CN202110736068.6A CN202110736068A CN115536544B CN 115536544 B CN115536544 B CN 115536544B CN 202110736068 A CN202110736068 A CN 202110736068A CN 115536544 B CN115536544 B CN 115536544B
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 159
- 238000002360 preparation method Methods 0.000 title abstract description 6
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 136
- 238000000034 method Methods 0.000 claims description 78
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 69
- 239000002904 solvent Substances 0.000 claims description 48
- 239000007789 gas Substances 0.000 claims description 36
- 239000011159 matrix material Substances 0.000 claims description 32
- 238000010521 absorption reaction Methods 0.000 claims description 25
- 239000002253 acid Substances 0.000 claims description 16
- 230000008569 process Effects 0.000 claims description 10
- 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
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 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
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 3
- 150000007522 mineralic acids Chemical class 0.000 claims description 3
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims 2
- 230000002745 absorbent Effects 0.000 abstract description 26
- 239000002250 absorbent Substances 0.000 abstract description 26
- 239000000654 additive Substances 0.000 abstract description 10
- 230000000996 additive effect Effects 0.000 abstract description 9
- 238000005265 energy consumption Methods 0.000 abstract description 8
- 238000000746 purification Methods 0.000 abstract description 8
- 230000008859 change Effects 0.000 abstract description 6
- 238000000926 separation method Methods 0.000 abstract description 5
- 239000000243 solution Substances 0.000 description 53
- 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 29
- 239000012071 phase Substances 0.000 description 23
- 230000008929 regeneration Effects 0.000 description 19
- 238000011069 regeneration method Methods 0.000 description 19
- 150000001412 amines Chemical class 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 238000012544 monitoring process Methods 0.000 description 6
- 229920000570 polyether Polymers 0.000 description 6
- 230000007704 transition Effects 0.000 description 6
- 239000004721 Polyphenylene oxide Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 125000000229 (C1-C4)alkoxy group Chemical group 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 238000004128 high performance liquid chromatography 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
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-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
- 238000004458 analytical method Methods 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- 238000005262 decarbonization Methods 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
- 150000002191 fatty alcohols Chemical class 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
- ZWRUINPWMLAQRD-UHFFFAOYSA-N nonan-1-ol Chemical compound CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical group [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-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
- 239000006096 absorbing agent Substances 0.000 description 1
- PBCJIPOGFJYBJE-UHFFFAOYSA-N acetonitrile;hydrate Chemical group O.CC#N PBCJIPOGFJYBJE-UHFFFAOYSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- -1 alcohol amine Chemical class 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
- 230000005587 bubbling Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000005261 decarburization Methods 0.000 description 1
- 238000001514 detection method Methods 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
- ZFDIRQKJPRINOQ-UHFFFAOYSA-N ethyl but-2-enoate Chemical compound CCOC(=O)C=CC ZFDIRQKJPRINOQ-UHFFFAOYSA-N 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- MCVVUJPXSBQTRZ-UHFFFAOYSA-N methyl but-2-enoate Chemical compound COC(=O)C=CC MCVVUJPXSBQTRZ-UHFFFAOYSA-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
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000035484 reaction time Effects 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 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 by this law 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, a preparation method and application thereof.
Background
The chemical absorption method is one of the most mature methods at present, but one common problem is that the regeneration energy consumption is high. In view of this problem, work is currently being conducted mainly from the aspects of new absorber development and process improvement or new process research, and the like.
Among them, the research ideas for new absorbents are mainly to develop new chemical absorbents. In recent years, some researchers change thinking modes and begin to research the phase change absorbent for decarburization process, so as to solve the problem of higher regeneration energy consumption. It is reported that the process can reduce the amount of liquid entering the regeneration tower and thus the regeneration energy consumption, compared to the conventional chemical absorption process, with the same treatment effect.
However, the phase change absorbent is used for decarbonization, and the problems that the separation process of the organic phase and the carrier phase in the rich liquid phase after absorption is slow, the regeneration process of the subsequent carrier phase is influenced, the absorption performance of the lean liquid after regeneration is influenced and the like are commonly existed due to the characteristics of the absorbent such as high viscosity and surface tension. The chemical demulsifier is added to ensure that the phase change absorbent after decarbonization can rapidly and thoroughly realize the transition from homogeneous phase to heterogeneous phase, and reduce the influence of intermediate transition state on the separation effect of the absorbent, thereby ensuring a series of continuous reactions of regeneration and absorption after the phase separation of the absorbent 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, and a preparation method and application thereof.
In order to achieve the above object, a first aspect of 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 by this law 1 R 2 CHR 3 (CH 2 ) n The number of CONHN structures is 2 m -one of the groups of 1, m being an integer from 1 to 20;
wherein R is 1 、R 2 And R is 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 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 demulsification function, the method comprising the steps of:
(1) In the presence of a first solvent, hydrazine and CR 1 R 2 ＝CR 3 (CH 2 ) n COOR 4 Performing first contact to obtain a first generation matrix compound; wherein R is 1 、R 2 、R 3 And R is 4 Each independently is H or C1-C4 alkyl, n is an integer from 0 to 6;
(2) Contacting the first generation of base compound with hydrazine in the presence of a second solvent to obtain a first generation of target compound;
(3) Optionally, contacting 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, fourth contacting the second generation base compound with hydrazine in the presence of a fourth solvent to obtain a second generation target compound;
(5) Optionally, repeating the step (3) and the step (4) on the basis of the rule to obtain a product containing the q-th generation target compound; wherein q is an integer of 3 to 20.
In a third aspect the present invention provides the use of a compound as hereinbefore defined, a process as hereinbefore defined or a product comprising a compound of interest as hereinbefore defined in the manufacture of a product for gas absorption, in particular acid gas absorption.
Compared with the prior art, the technical scheme provided by the invention has at least 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-type and high order. From the molecular structure, the compound is obtained by continuously repeating the radial growth of the Y type outwards from a double-core molecule (hydrazine), and the structure is similar to that of the Y type compound. When the compound is used as an additive of a gas absorbent (especially an acid gas absorbent), the absorbent after absorbing gas (especially acid gas) can effectively break the interfacial property of an organic phase-carrier phase, namely break the interfacial balance, quickly realize the transition from homogeneous phase to heterogeneous phase, reduce the influence of an intermediate transition state on the separation effect of the absorbent, thereby ensuring a series of continuous reactions of regeneration and absorption after the phase separation of the absorbent and improving the gas purification efficiency.
(2) The method for preparing the compound has the advantages of simple steps, high efficiency, environmental friendliness, higher yield and purity and contribution to industrialization.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The first aspect of the invention provides a compound with demulsification function, which has a structure shown as 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 by this law 1 R 2 CHR 3 (CH 2 ) n The number of CONHN structures is 2 m -one of the groups of 1, m being an integer from 1 to 20;
wherein R is 1 、R 2 And R is 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 are H and A 1 -A 4 At least one of them contains-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 straight-chain 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 by this law 1 R 2 CHR 3 (CH 2 ) n The number of 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 is 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.ltoreq.5.
According to some embodiments of the invention, M is NHNH 2 。
According to some embodiments of the invention, A 1 -A 4 Identical 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 The method comprises the steps of carrying out a first treatment on the surface of the Or,
A 1 -A 4 identical and is-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 The method comprises the steps of carrying out a first treatment on the surface of the Or,
A 1 -A 4 identical 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 The method comprises the steps of carrying out a first treatment on the surface of the Or,
A 1 -A 4 identical and CR 1 R 2 CHR 3 (CH 2 ) n The number of CONHN structures is 2 m -1, wherein R 1 ＝H，R 2 ＝H，R 3 =h, n is 0, m is 1, m is NHNH 2 The method comprises the steps of carrying out a first treatment on the surface of the Or,
A 1 -A 4 identical and CR 1 R 2 CHR 3 (CH 2 ) n The number of CONHN structures is 2 m -1, wherein R 1 ＝H，R 2 ＝H，R 3 =h, n is 1, m is NHNH 2 The method comprises the steps of carrying out a first treatment on the surface of the Or,
A 1 -A 4 identical and CR 1 R 2 CHR 3 (CH 2 ) n The number of CONHN structures is 2 m -1, wherein R 1 ＝Me，R 2 ＝H，R 3 =h, n is 0, m is 1, m is NHNH 2 The method comprises the steps of carrying out a first treatment on the surface of the Or,
A 1 -A 4 identical and CR 1 R 2 CHR 3 (CH 2 ) n The number of CONHN structures is 2 m -1, wherein R 1 ＝H，R 2 ＝H，R 3 =h, n is 0, m is 2, m is NHNH 2 The method comprises the steps of carrying out a first treatment on the surface of the Or,
A 1 -A 4 identical and CR 1 R 2 CHR 3 (CH 2 ) n The number of CONHN structures is 2 m -1, wherein R 1 ＝H，R 2 ＝H，R 3 =h, n is 1, m is 2,m is NHNH 2 The method comprises the steps of carrying out a first treatment on the surface of the Or,
A 1 -A 4 identical and CR 1 R 2 CHR 3 (CH 2 ) n The number of CONHN structures is 2 m -1, wherein R 1 ＝Me，R 2 ＝H，R 3 =h, n is 0, m is 2, m is NHNH 2 The method comprises the steps of carrying out a first treatment on the surface of the Or,
A 1 -A 4 identical and CR 1 R 2 CHR 3 (CH 2 ) n The number of CONHN structures is 2 m -1, wherein R 1 ＝H，R 2 ＝H，R 3 =h, n is 0, m is 3, m is NHNH 2 The method comprises the steps of carrying out a first treatment on the surface of the Or,
A 1 -A 4 identical and CR 1 R 2 CHR 3 (CH 2 ) n The number of CONHN structures is 2 m -1, wherein R 1 ＝H，R 2 ＝H，R 3 =h, n is 1, m is 3, m is NHNH 2 The method comprises the steps of carrying out a first treatment on the surface of the Or,
A 1 -A 4 identical and CR 1 R 2 CHR 3 (CH 2 ) n The number of CONHN structures is 2 m -1, wherein R 1 ＝Me，R 2 ＝H，R 3 =h, n is 0, m is 3, m is NHNH 2 The method comprises the steps of carrying out a first treatment on the surface of the Or,
A 1 -A 4 identical and CR 1 R 2 CHR 3 (CH 2 ) n The number of CONHN structures is 2 m -1, wherein R 1 ＝H，R 2 ＝H，R 3 =h, n is 0, m is 4, m is NHNH 2 The method comprises the steps of carrying out a first treatment on the surface of the Or,
A 1 -A 4 identical and CR 1 R 2 CHR 3 (CH 2 ) n The number of CONHN structures is 2 m -1, wherein R 1 ＝H，R 2 ＝H，R 3 =h, n is 1, m is 4, m is NHNH 2 The method comprises the steps of carrying out a first treatment on the surface of the Or,
A 1 -A 4 identical and CR 1 R 2 CHR 3 (CH 2 ) n The number of CONHN structures is 2 m -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 principle of Michael addition reaction, grafting groups (e.g., acrylate chains) of different lengths can be reacted with hydrazine (as an initiating core) to be able to repeatedly grow radially outwards continuously, thus obtaining compounds containing different or same substituted grafting groups, which can be well used in gas absorption. However, it is preferable to graft with the same grafting group to obtain a highly symmetrical molecule similar to the Y-type compound, in view of cost and ease of handling.
Accordingly, in a second aspect the present invention provides a method of preparing a compound having a demulsification function, the method comprising the steps of:
(1) In the presence of a first solvent, hydrazine and CR 1 R 2 ＝CR 3 (CH 2 ) n COOR 4 Performing a first contact to obtain a first generation base compound (1G base compound); wherein R is 1 、R 2 、R 3 And R is 4 Each independently is H or C1-C4 alkyl, n is an integer from 0 to 6;
(2) Subjecting the first-generation base compound to a second contact with hydrazine in the presence of a second solvent to obtain a first-generation target compound (1G target compound);
(3) Optionally, contacting the first generation target compound with CR in the presence of a third solvent 1 R 2 ＝CR 3 (CH 2 ) n COOR 4 Performing 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 obtain a second-generation target compound (2G target compound);
(5) Optionally, repeating the step (3) and the step (4) on the basis of the rule to obtain a product containing the q-th 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 is 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 invention, in step (1), the first solvent may be selected from water and/or a C1-C4 alcohol, preferably methanol and/or water.
According to some embodiments of the invention, the first solvent may be used in an amount of 2-20mL, preferably 3-15mL, relative to 1g of hydrazine.
According to some embodiments of the invention, in step (1), CR is performed to make the reaction proceed better 1 R 2 ＝CR 3 (CH 2 ) n COOR 4 With the amount of hydrazine, 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 contact is in the form of: adding hydrazine and/or hydrazine solution into CR at 20-40deg.C 1 R 2 ＝CR 3 (CH 2 ) n COOR 4 In solution.
In the present invention, in the step (1), the hydrazine solution is obtained by dissolving hydrazine in the first solvent; the CR is 1 R 2 ＝CR 3 (CH 2 ) n COOR 4 Solution from CR 1 R 2 ＝CR 3 (CH 2 ) n COOR 4 Dissolving in the first solvent to obtain the product; there is no particular requirement for the amount of the first solvent for dissolution, as long as the requirements of the present invention can be satisfied.
According to some embodiments of the invention, in step (1), the addition rate of the hydrazine and/or the hydrazine solution is required to be in a range of preferably 1 to 10mL/min, more preferably 1 to 5mL/min, relative to 100mL of the hydrazine and/or the hydrazine solution, in order to obtain a better effect.
According to some embodiments of the invention, the first contact time may be 12-72 hours, preferably 24-48 hours. Wherein, when hydrazine and/or hydrazine solution starts to be added dropwise, the hydrazine and CR 1 R 2 ＝CR 3 (CH 2 ) n COOR 4 The reaction starts to take place.
According to some embodiments of the invention, in step (2), the second solvent may be selected from water and/or a C1-C4 alcohol, preferably methanol and/or water.
According to some embodiments of the invention, the second solvent may be used in an amount of 2-20mL, preferably 3-15mL, relative to 1g of hydrazine.
According to some embodiments of the invention, in step (2), there is a requirement for the amount of first generation base compound and hydrazine to be used in order to allow the reaction to 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 ℃.
In the present invention, in the step (2), the hydrazine solution is obtained by dissolving hydrazine in the second solvent; the solution of the first generation matrix compound is obtained by dissolving the first generation matrix compound in the second solvent; there is no particular requirement for the amount of the second solvent for dissolution, as long as the requirements of the present invention can be satisfied.
According to some embodiments of the invention, in step (2), the rate of addition of the solution of the first generation base compound is required in order to allow the reaction to proceed better, preferably at a rate of 1 to 20mL/min, more preferably 1 to 10mL/min, relative to 100mL of the solution of the first generation base compound.
According to some embodiments of the invention, the second contact time may be 12-72 hours, preferably 24-48 hours. Wherein when the solution of the first-generation base compound starts to be added dropwise, the first-generation base compound starts to react with hydrazine.
According to some embodiments of the invention, in step (3), the first generation target compound is reacted with CR in order to make the reaction proceed better 1 R 2 ＝CR 3 (CH 2 ) n COOR 4 The amount of (C) is required, and CR is preferred 1 R 2 ＝CR 3 (CH 2 ) n COOR 4 Excess, e.g. of the first generation target compound with CR 1 R 2 ＝CR 3 (CH 2 ) n COOR 4 The molar ratio of (2) 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 CR at 20-40deg.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 is 1 R 2 ＝CR 3 (CH 2 ) n COOR 4 Solution from CR 1 R 2 ＝CR 3 (CH 2 ) n COOR 4 Dissolving in the third solvent to obtain the product; the amount of the third solvent to be 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 make the reaction proceed better, there is a certain requirement for the addition rate of the solution of the first-generation target compound, preferably, the addition rate is 1 to 20mL/min, more preferably, 1 to 10mL/min, with respect to 100mL of the solution of the first-generation target compound.
According to some embodiments of the invention, the third contact time is 12-72 hours, preferably 24-48 hours. Wherein, when the solution of the first-generation target compound starts to be added dropwise, the first-generation target compoundTarget compound and CR 1 R 2 ＝CR 3 (CH 2 ) n COOR 4 The reaction starts to take place.
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 invention, in step (4), there is a requirement for the amount of second-generation base compound and hydrazine, and preferably, the amount of hydrazine is in excess, the molar ratio of second-generation base compound to hydrazine being 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 matrix compound is added to the hydrazine and/or hydrazine solution at 20-40 ℃.
In the present invention, in the step (4), the hydrazine solution is obtained by dissolving hydrazine in the fourth solvent; the second-generation matrix compound solution is obtained by dissolving the second-generation matrix compound in the fourth solvent; the amount of the fourth solvent to be 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 invention, the fourth contact time may be 12-72 hours, preferably 24-48 hours. Wherein when the solution of the second-generation base compound starts to be added dropwise, the second-generation base compound starts to react with hydrazine.
According to some embodiments of the invention, the fourth solvent may be used in an amount of 2-20mL, preferably 3-15mL, relative to 1g of hydrazine.
According to some embodiments of the invention, in step (4), the rate of addition of the solution of the second-generation base compound is required in order to allow the reaction to proceed better, preferably at a rate of 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 used and the time of contact in the repetition of 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, step (1) and step (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 From 0.1 to 1% by weight.
In the present invention, the method preferably further comprises a step of purification, for example, in step (1), the reaction liquid 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 requirement of the present invention can be satisfied, and for example, the following steps can be performed: the reaction liquid after the first contact is distilled for 10 to 20 hours under reduced pressure at the temperature of 30 to 50 ℃ and the vacuum degree of 50 to 70 kPa.
In the present invention, the step (2) preferably further comprises a second post-treatment (purification treatment) of the reaction solution after the second contact. The step of the second post-treatment is not particularly limited as long as the requirement of the present invention can be satisfied, and for example, the following steps can be performed: and (3) carrying out reduced pressure distillation on the reaction solution after the second contact for 10-30h at the temperature of 40-80 ℃ and the vacuum degree of 60-90 kPa.
Similarly, step (3), step (4) and step (5) may 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 may be used as an additive (demulsifier) directly or after a simple solvent removal step (e.g., 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 can be 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 an organic amine, a polyether and a 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 present invention, the absorbent is selected from the group consisting of organic amines and polyethers.
In the present invention, the organic amine is contained in an amount of 1 to 50wt%, the polyether is contained in an amount of 40 to 99wt%, and the additive is contained in an amount of 0.005 to 10wt%, based on the total weight of the absorbent and the additive in the composition.
In the present invention, the organic amine is contained in an amount of 5 to 50wt%, the polyether is contained in an amount of 45 to 95wt%, and the additive is contained in an amount of 0.01 to 5wt%, based on the total weight of the absorbent and the additive in the composition.
In the invention, the organic amine is alcohol amine of C1-C6, and is at least one selected from monoethanolamine, diethanolamine, triethanolamine, 3-propanolamine, monoisopropanolamine, diisopropanolamine and triisopropanolamine, preferably at least one selected from 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 polyethylene glycol dimethyl ether and/or polyethylene glycol monomethyl ether.
Wherein the C7-C10 fatty alcohol can be, for example, n-heptanol, n-octanol, nonanol or decanol.
In a third aspect, the present invention provides the use of the compound, the method and the compound having a demulsification function (particularly a product containing a target compound (including at least one of a first generation target compound, a second generation target compound, … … and a q-th generation target compound)) in gas absorption, particularly in acid gas absorption.
According to some embodiments of the invention, the acid gas is an inorganic acid gas, preferably at least one selected from carbon dioxide, sulfur dioxide and hydrogen sulfide.
In the present inventionThe parameters measured during regeneration are the acid gas value in the carrier phase, i.e. the absorption of CO in the carrier phase 2 Relative content (V) CO2 /V Solution ，mL/mL)。
The present invention will be described in detail by examples.
In the following examples, all materials were commercially available unless otherwise specified.
Monitoring the progress of the reaction by HPLC; yield = conversion x selectivity;
conversion = percentage of the amount of reactant taking part in the reaction (amount of reactant of raw material) to the amount entering the reactor (initial amount of raw material);
selectivity = amount of key components consumed (mol) to produce target product/amount of key components involved in reaction (mol); purity was detected by HPLC;
analysis conditions for HPLC: the column was a Phenomnex C18 column (250 mm. Times.4.6 mm,4 μm); the mobile phase is acetonitrile-water (volume ratio of 70:30), the detection wavelength is 350nm, the flow rate is 0.8mL/min, and the sample injection amount is 20 mu L.
Example 1
1G matrix compound:
1G target compound:
(1) 344.36g of Methyl Acrylate (MA) was dissolved in 100mL of methanol in a three-necked flask, and 3.5g of hydroquinone monomethyl ether was added to obtain a methanol solution (MA solution) of methyl acrylate; then 16.02g of hydrazine (AH) was dissolved in 50mL of methanol to give a methanol solution of hydrazine (AH solution), and the AH solution was placed in a constant pressure dropping funnel; slowly dropwise adding an AH solution into the MA solution under the stirring of 25 ℃ for 0.5h, wherein MA: the molar ratio of AH is 8:1, and then the heat preservation reaction is continued for 24 hours; after monitoring the completion of the reaction, the reacted product was distilled under reduced pressure at 35℃and a vacuum degree of 60kPa for 16 hours to remove methanol and excess MA, and the obtained pale yellow product was 1G base compound with a purity of 98.5% by weight and a yield of 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-port reaction bottle to ensure that the molar ratio of AH to the 1G matrix compound is 16:1, a step of; slowly dropwise adding a methanol solution of a 1G matrix compound under stirring at 25 ℃ for 0.5h, keeping the temperature for 24h, monitoring the reaction, distilling the reacted product under reduced pressure at 55 ℃ and a vacuum degree of 80kPa for 16h to remove methanol and excessive AH, and finally obtaining a 1G target compound as a pale yellow viscous liquid with the viscosity of 95.2wt% and the yield of 87.1% in a distillation flask.
Example 2
2G matrix compound:
2G target compound:
repeating steps (1) and (2) in preparation example 1 to obtain a 1G base compound and a 1G target compound, respectively;
(3) According to the mode of the step (1), 137.74g of Methyl Acrylate (MA) is dissolved in 100mL of methanol in a three-neck flask, and 0.2g of hydroquinone monomethyl ether is added to obtain a methanol solution (MA solution) of methyl acrylate; then, 37.6G of the 1G target compound was dissolved in 50mL of methanol to obtain a methanol solution of the 1G target compound, which was placed in a constant pressure dropping funnel; slowly dropwise adding a methanol solution of the 1G target compound into the MA solution under the stirring of 25 ℃ for 0.5h, wherein the molar ratio of the MA to the 1G target compound is 16:1, and then continuing to perform heat preservation reaction for 24h; after monitoring the completion of the reaction, the reacted product was distilled under reduced pressure at 35℃and a vacuum degree of 60kPa for 16 hours to remove methanol and excess MA, and the obtained pale yellow product was a 2G base compound with a purity of 98.3% by weight and a yield of 80.0%.
(4) Dissolving the 2G matrix product obtained in the step (3) in 100mL of methanol, placing the 2G matrix compound in 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-port reaction bottle to ensure that the molar ratio of AH to the 2G matrix compound is 16:1, a step of; slowly dropwise adding a methanol solution of a 2G matrix compound under stirring at 25 ℃ for 1h, keeping the temperature for 24h, monitoring the reaction, distilling the reacted product under reduced pressure at 55 ℃ and a vacuum degree of 80kPa for 16h to remove methanol and excessive AH, and finally obtaining a 2G target compound as a pale yellow viscous liquid with the purity of 93.6wt% and the yield of 71.3% after the viscosity in a distillation bottle becomes large.
Example 3
3G matrix compound:
3G target compound:
repeating steps (3) and (4) using the 2G target compound as a reactant, as in example 2, yields a 3G base compound and a 3G target compound.
Wherein, the purity of the 3G matrix compound is 97.6 weight percent, and the yield is 65.7 percent; the 3G target compound was 93.2wt% pure and the yield was 55.8%.
Example 4
Repeating steps (3) and (4) using the 3G target compound as a reactant, as in example 3, yields a 4G base compound and a 4G target compound.
Wherein, the purity of the 4G matrix compound is 97.2 weight percent, and the yield is 49.1 percent; the purity of the 4G target compound was 92.8wt% and the yield was 42.3%.
Example 5
Repeating steps (3) and (4) using the 2G target compound as a reactant, as in example 4, produced a 5G base compound and a 5G target compound.
Wherein, the purity of the 5G matrix compound is 96.3 weight percent, and the yield is 37.2 percent; the purity of the 5G target compound was 92.2wt% and the yield was 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 was 98.4wt% pure with a yield of 92.5%; the purity of the 1G target compound was 95.8wt% and the yield was 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 butenoate.
Finally, the 1G base compound was 98.2wt% pure with a yield of 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 344.36g of Methyl Acrylate (MA) are replaced by 456.56g of ethyl butenoate.
Finally, the 1G base compound was 98.8wt% pure with a yield of 91.4%; the purity of the 1G target compound was 93.2wt% and the yield was 82.3%.
The following test examples are presented to illustrate the use of the compounds prepared in the above examples for acid gas absorption
The organic amine, polyether and additives were formulated into a composition at the levels shown in Table 1 and formulated into an acid gas absorbent (water as solvent) of the organic amine at a molar concentration of 3 mol/L. Wherein the weight average molecular weight of the polyethylene glycol dimethyl ether used is 260; polyoxyethylene polyoxypropylene stearyl ether was purchased from Daqing chemical Co., ltd.
Gas absorption experiments: feed gas (acid gas CO) 2 12.8% by volume) is passed through a moisture absorbing bottle and a buffer bottle, and then enters an absorption tube filled with absorbent at 40 ℃ +/-0.5 ℃, wherein the gas flow of raw material gas is controlled to be 100mL/min, bubbling absorption is carried out, the absorption temperature is controlled by a constant temperature tank, and after a period of time, CO in the tail gas is discharged 2 And monitoring and analyzing the content by adopting a flue gas analyzer, then closing an air source, and taking a carrier phase after absorbing the acid gas for liquid phase analysis. Wherein, a feed gas pipeline is reserved for adjusting the acid gas content in the feed gas. Wherein the CO absorbed in the absorbent is generated by gas generation method 2 Analyzing, specifically, taking a certain amount of sample, placing into a neutralization reaction bottle, taking excessive dilute sulfuric acid solution, placing into a straight tube in the reaction bottle, covering a plug, and recording the reading V when the liquid level of the solution bottle is equal to that of the straight tube with scales o . The liquid in the reaction bottle is contacted and reacted, CO 2 Precipitating, and recording and reading the book V when the two liquid levels are in phase 1 。V 1 And V is equal to o The difference is the CO generated after the reaction 2 The volume, from which the CO in the solution can be back calculated 2 The content is as follows.
Regeneration experiment: and (3) taking the carrier phase for a regeneration test after the absorption reaction is finished according to the absorption reaction time of 6 hours. Wherein, the regeneration temperature is controlled to be 110 ℃, the rotating speed of mechanical stirring is 150rpm, the power of a heating device is 1000W, and the device stops after 30min, and the CO in the solution is measured 2 Content to determine desorbed CO 2 Is a combination of the amounts of (a) and (b).
The results of the gas absorption experiment and the regeneration experiment of the above test examples and comparative test examples are shown in Table 2.
TABLE 1
TABLE 2
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In table 2, t1 represents "time for first occurrence of carrier phase droplet settling after aeration", and a smaller t1 indicates a stronger ability of the absorbent to undergo phase transition, i.e., a more easy occurrence of phase transition; t2 represents the time for thoroughly separating the carrier phase from the organic phase after the absorption reaction is finished, and the smaller t2 indicates that the better the effect of the phase change process of the absorbent is, the lower the energy consumption of the absorbent regeneration is;
regeneration energy consumption means "per unit volume of CO regenerated 2 The energy consumption required to be consumed is calculated as follows: regeneration energy consumption=1×30×60/(L) 0 -L 30 ) Units kJ/mL; wherein L is 0 The initial (0 min regeneration) sour gas value in the carrier phase during regeneration; l (L) 30 The sour gas value at 30min in the carrier phase during regeneration is indicated.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (35)
1. A compound with demulsification function is characterized in that the compound has a structure shown in a formula (I),
wherein,
A 1 -A 4 each independently is-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 CO M) 2 ) 2 And CR derived by this law 1 R 2 CHR 3 (CH 2 ) n The number of CONHN structures is 2 m -one of the groups of 1, m being an integer from 1 to 10;
wherein R is 1 、R 2 And R is 3 Each independently is H or C1-C4 alkyl, n is an integer from 0 to 6, M is NHNH 2 ；
Wherein A is 1 -A 4 All contain-NHNH 2 。
2. The compound of claim 1, wherein R 1 、R 2 And R is 3 Each independently is one of H, methyl and ethyl;
and/or n is an integer from 0 to 4;
and/or m.ltoreq.5.
3. The compound according to claim 1 or 2, wherein a 1 -A 4 Identical 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 The method comprises the steps of carrying out a first treatment on the surface of the Or,
A 1 -A 4 identical and is-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 The method comprises the steps of carrying out a first treatment on the surface of the Or,
A 1 -A 4 identical 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 The method comprises the steps of carrying out a first treatment on the surface of the Or,
A 1 -A 4 identical and CR 1 R 2 CHR 3 (CH 2 ) n The number of CONHN structures is 2 m -1, wherein R 1 ＝H，R 2 ＝H，R 3 =h, n is 0, m is 1, m is NHNH 2 The method comprises the steps of carrying out a first treatment on the surface of the Or,
A 1 -A 4 identical and CR 1 R 2 CHR 3 (CH 2 ) n The number of CONHN structures is 2 m -1, wherein R 1 ＝H，R 2 ＝H，R 3 =h, n is 1, m is NHNH 2 The method comprises the steps of carrying out a first treatment on the surface of the Or,
A 1 -A 4 identical and CR 1 R 2 CHR 3 (CH 2 ) n The number of CONHN structures is 2 m -1, wherein R 1 ＝Me，R 2 ＝H，R 3 =h, n is 0, m is 1, m is NHNH 2 The method comprises the steps of carrying out a first treatment on the surface of the Or,
A 1 -A 4 identical and CR 1 R 2 CHR 3 (CH 2 ) n The number of CONHN structures is 2 m -1, wherein R 1 ＝H，R 2 ＝H，R 3 =h, n is 0, m is 2, m is NHNH 2 The method comprises the steps of carrying out a first treatment on the surface of the Or,
A 1 -A 4 identical and CR 1 R 2 CHR 3 (CH 2 ) n The number of CONHN structures is 2 m -1, wherein R 1 ＝H，R 2 ＝H，R 3 =h, n is 1, m is 2, m is NHNH 2 The method comprises the steps of carrying out a first treatment on the surface of the Or,
A 1 -A 4 identical and CR 1 R 2 CHR 3 (CH 2 ) n The number of CONHN structures is 2 m -1, wherein R 1 ＝Me，R 2 ＝H，R 3 =h, n is 0, m is 2, m is NHNH 2 The method comprises the steps of carrying out a first treatment on the surface of the Or,
A 1 -A 4 identical and CR 1 R 2 CHR 3 (CH 2 ) n The number of CONHN structures is 2 m -1, wherein R 1 ＝H，R 2 ＝H，R 3 ＝H，n is 0, m is 3, M is NHNH 2 The method comprises the steps of carrying out a first treatment on the surface of the Or,
A 1 -A 4 identical and CR 1 R 2 CHR 3 (CH 2 ) n The number of CONHN structures is 2 m -1, wherein R 1 ＝H，R 2 ＝H，R 3 =h, n is 1, m is 3, m is NHNH 2 The method comprises the steps of carrying out a first treatment on the surface of the Or,
A 1 -A 4 identical and CR 1 R 2 CHR 3 (CH 2 ) n The number of CONHN structures is 2 m -1, wherein R 1 ＝Me，R 2 ＝H，R 3 =h, n is 0, m is 3, m is NHNH 2 The method comprises the steps of carrying out a first treatment on the surface of the Or,
A 1 -A 4 identical and CR 1 R 2 CHR 3 (CH 2 ) n The number of CONHN structures is 2 m -1, wherein R 1 ＝H，R 2 ＝H，R 3 =h, n is 0, m is 4, m is NHNH 2 The method comprises the steps of carrying out a first treatment on the surface of the Or,
A 1 -A 4 identical and CR 1 R 2 CHR 3 (CH 2 ) n The number of CONHN structures is 2 m -1, wherein R 1 ＝H，R 2 ＝H，R 3 =h, n is 1, m is 4, m is NHNH 2 The method comprises the steps of carrying out a first treatment on the surface of the Or,
A 1 -A 4 identical and CR 1 R 2 CHR 3 (CH 2 ) n The number of CONHN structures is 2 m -1, wherein R 1 ＝Me，R 2 ＝H，R 3 =h, n is 0, m is 4, m is NHNH 2 。
4. A process for preparing a compound having a demulsification function as claimed in any one of claims 1 to 3, which comprises the steps of:
(1) In the presence of a first solvent, hydrazine and CR 1 R 2 ＝CR 3 (CH 2 ) n COOR 4 Carrying out first contact to obtain a product containing a first generation matrix compound;wherein R is 1 、R 2 、R 3 And R is 4 Each independently is H or C1-C4 alkyl, n is an integer from 0 to 6;
(2) Contacting the product comprising the first generation of the base compound with hydrazine in the presence of a second solvent to produce a product comprising the first generation of the target compound;
(3) Optionally, contacting the product comprising 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 product containing a second-generation matrix compound;
(4) Optionally, in the presence of a fourth solvent, fourth contacting the product comprising the second-generation base compound with hydrazine to obtain a product comprising the second-generation target compound;
(5) Optionally, repeating the step (3) and the step (4) on the basis of the rule to obtain a product containing the q-th generation target compound; wherein q is an integer of 3 to 10.
5. The method of claim 4, wherein R 1 、R 2 、R 3 And R is 4 Each independently is one of H, methyl and ethyl, and/or n is an integer from 0 to 4.
6. The method according to claim 4 or 5, wherein in step (1), the first solvent is selected from water and/or a C1-C4 alcohol;
and/or, the first solvent is used in an amount of 2 to 20mL relative to 1g of hydrazine;
and/or CR 1 R 2 ＝CR 3 (CH 2 ) n COOR 4 The molar ratio of the catalyst to hydrazine is (4-12): 1, a step of;
and/or, the first contact mode is that: adding hydrazine and/or hydrazine solution into CR at 20-40deg.C 1 R 2 ＝CR 3 (CH 2 ) n COOR 4 In solution;
and/or the time of the first contact is 12-72h.
7. The method of claim 6, wherein the first solvent is methanol and/or water.
8. The method of claim 6, wherein the first solvent is used in an amount of 3-15mL relative to 1g of hydrazine.
9. The method of claim 6, wherein the CR 1 R 2 ＝CR 3 (CH 2 ) n COOR 4 The molar ratio of the catalyst to hydrazine is (6-10): 1.
10. the method according to claim 6, wherein the rate of addition is 1-10mL/min relative to 100mL of hydrazine and/or hydrazine solution.
11. The method of claim 10, wherein the rate of addition is 1-5mL/min relative to 100mL of hydrazine and/or hydrazine solution.
12. The method of claim 6, wherein the first contact is for a period of 24-48 hours.
13. The method according to claim 4 or 5, wherein in step (2), the second solvent is selected from water and/or a C1-C4 alcohol;
and/or, the second solvent is used in an amount of 2 to 20mL relative to 1g of hydrazine;
and/or the molar ratio of hydrazine to the first generation base compound is (4-20): 1, a step of;
and/or, the second contact mode is that: the solution of the first generation matrix compound is added to the hydrazine and/or hydrazine solution at 20-40 ℃.
14. The method of claim 13, wherein the second solvent is methanol and/or water.
15. The method of claim 13, wherein the second solvent is used in an amount of 3-15mL relative to 1g of hydrazine.
16. The method of claim 13, wherein the molar ratio of hydrazine to the first generation base compound is (8-16): 1.
17. the method of claim 13, wherein the rate of addition is 1-20mL/min relative to 100mL of the solution of the first generation matrix compound.
18. The method of claim 17, wherein the rate of addition is 1-10mL/min relative to 100mL of the solution of the first generation matrix compound.
19. The method of claim 13, wherein the second contacting is for a period of 12-72 hours.
20. The method of claim 19, wherein the second contacting is for a period of 24-48 hours.
21. The method according to claim 4 or 5, wherein in step (3), the first generation target compound is combined with CR 1 R 2 ＝CR 3 (CH 2 ) n COOR 4 The molar ratio of (2) is 1: (8-20);
and/or, the third contact mode is that: adding a solution of the first generation target compound to CR at 20-40deg.C 1 R 2 ＝CR 3 (CH 2 ) n COOR 4 In solution;
and/or, the time of the third contact is 12-72h;
and/or, the third solvent is used in an amount of 2 to 20mL relative to 1g of the first-generation target compound;
and/or, in step (4), the molar ratio of the second-generation matrix compound to hydrazine is 1: (16-32);
and/or, the fourth contact mode is that: the second contact mode is as follows: adding a solution of the second generation matrix compound to the hydrazine and/or hydrazine solution at 20-40 ℃;
and/or, the fourth contact time is 12-72h; and/or, the fourth solvent is used in an amount of 2 to 20mL relative to 1g of hydrazine.
22. The method of claim 21, wherein the first generation target compound is conjugated to CR 1 R 2 ＝CR 3 (CH 2 ) n COOR 4 The molar ratio of (2) is 1: (12-18).
23. The method of claim 21, wherein the rate of addition is 1-20mL/min relative to 100mL of the solution of the first generation target compound.
24. The method of claim 23, wherein the rate of addition is 1-10mL/min relative to 100mL of the solution of the first generation target compound.
25. The method of claim 21, wherein the third contacting is for a period of 24-48 hours.
26. The method of claim 21, wherein the third solvent is used in an amount of 3-15mL relative to 1g of the first generation target compound.
27. The method of claim 21, wherein the molar ratio of the second-generation base compound to hydrazine is 1: (18-24).
28. The method of claim 21, wherein the fourth contacting is for a period of 24-48 hours.
29. The method of claim 21, wherein the fourth solvent is used in an amount of 3-15mL relative to 1g of hydrazine.
30. The method of claim 21, wherein the rate of addition is 1-20mL/min relative to 100mL of the solution of the second generation base compound.
31. The method of claim 30, wherein the rate of addition is 1-10mL/min relative to 100mL of the solution of the second generation base compound.
32. Use of a compound according to any one of claims 1 to 3, a process according to any one of claims 4 to 31 and a product comprising a compound of interest prepared by a process according to any one of claims 4 to 31 in gas absorption.
33. The use according to claim 32, wherein the use is in acid gas absorption.
34. The use of claim 33, wherein the acid gas is an inorganic acid gas.
35. The use of claim 34, wherein the inorganic acid gas is selected from at least one of carbon dioxide, sulfur dioxide, and hydrogen sulfide.
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