CN111905804A - HZB salt-inhibiting desulfurizing agent - Google Patents
HZB salt-inhibiting desulfurizing agent Download PDFInfo
- Publication number
- CN111905804A CN111905804A CN202010806695.8A CN202010806695A CN111905804A CN 111905804 A CN111905804 A CN 111905804A CN 202010806695 A CN202010806695 A CN 202010806695A CN 111905804 A CN111905804 A CN 111905804A
- Authority
- CN
- China
- Prior art keywords
- salt
- inhibiting
- hzb
- diethylene glycol
- desulfurizer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 150000003839 salts Chemical class 0.000 title claims abstract description 21
- 230000002401 inhibitory effect Effects 0.000 title claims abstract description 19
- 230000003009 desulfurizing effect Effects 0.000 title claims description 8
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 230000003197 catalytic effect Effects 0.000 claims abstract description 9
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000007524 organic acids Chemical class 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 6
- 238000009835 boiling Methods 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims abstract description 4
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims abstract 12
- CDFFPIHYQLOEHR-UHFFFAOYSA-N 2-(2-hydroxyethoxy)-1-morpholin-4-ylethanol Chemical compound OCCOCC(O)N1CCOCC1 CDFFPIHYQLOEHR-UHFFFAOYSA-N 0.000 claims abstract 4
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 6
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- 239000005711 Benzoic acid Substances 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 150000007513 acids Chemical class 0.000 claims description 3
- 235000010233 benzoic acid Nutrition 0.000 claims description 3
- 235000015165 citric acid Nutrition 0.000 claims description 3
- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical compound [Co+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 claims description 3
- UZVGFAUPMODEBR-UHFFFAOYSA-L disodium;9,10-dioxoanthracene-1,2-disulfonate Chemical compound [Na+].[Na+].C1=CC=C2C(=O)C3=C(S([O-])(=O)=O)C(S(=O)(=O)[O-])=CC=C3C(=O)C2=C1 UZVGFAUPMODEBR-UHFFFAOYSA-L 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 235000019260 propionic acid Nutrition 0.000 claims description 3
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 3
- 238000010494 dissociation reaction Methods 0.000 claims description 2
- 230000005593 dissociations Effects 0.000 claims description 2
- 229910000975 Carbon steel Inorganic materials 0.000 abstract description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 abstract description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 abstract description 3
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 abstract description 3
- 239000010962 carbon steel Substances 0.000 abstract description 3
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 abstract description 3
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 abstract description 3
- 238000005260 corrosion Methods 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 12
- 238000006477 desulfuration reaction Methods 0.000 description 7
- 230000023556 desulfurization Effects 0.000 description 7
- MSKCZPNQMQPOLH-UHFFFAOYSA-N 2-(2-hydroxyethoxy)-1,1-dimorpholin-4-ylethanol Chemical compound C1COCCN1C(O)(COCCO)N1CCOCC1 MSKCZPNQMQPOLH-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000004075 alteration Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 150000004698 iron complex Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- -1 sulfate radicals Chemical class 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0244—Nitrogen containing compounds with nitrogen contained as ring member in aromatic compounds or moieties, e.g. pyridine
-
- 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
- B01D53/86—Catalytic processes
- B01D53/8603—Removing sulfur compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
- B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Environmental & Geological Engineering (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Analytical Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Biomedical Technology (AREA)
- Health & Medical Sciences (AREA)
- Gas Separation By Absorption (AREA)
Abstract
The invention discloses a HZB salt-inhibiting desulfurizer, which relates to the technical field of desulfurizer and comprises a mixture of main raw materials of monomorpholinyl diethylene glycol and dimorpholinyl diethylene glycol or a high-boiling residue of monomorpholinyl diethylene glycol or dimorpholinyl diethylene glycol or morpholine; the main raw material is fully mixed and reacted with relevant organic acid with PK value more than 2.5 and appropriate participators to generate a catalytic salt-inhibiting desulfurizer; the HZB salt-inhibiting desulfurizer of the invention can completely avoid the generation of thiosulfate and sulfate and thiocyanate, can effectively remove sulfide, has wide application, low cost and stable chemical property, and has an anti-corrosion function on carbon steel equipment.
Description
Technical Field
The invention relates to the technical field of desulfurizing agents, in particular to a HZB salt-inhibiting desulfurizing agent.
Background
The sulfide in the wide chemical industry raw material gas, industrial exhaust gas and fuel gas is required to be efficiently removed, and the generation of double salts such as thiosulfate, sulfate, thiocyanate and the like in the desulfurization process greatly influences the environment, the efficiency and the cost of the process.
Many of the commonly developed desulfurization techniques, such as adding respective catalytic desulfurization agents, such as ADA and PDS, to an aqueous solution of sodium carbonate or an aqueous solution of ammonia, but none of them has the ability to inhibit the formation of double salts, and the recently developed iron complex method and the catalytic desulfurization agent of DSH comprising a water-soluble iron salt, manganese salt, zinc salt, nickel salt and an organic complexing agent are said to have the effect of inhibiting salts during the desulfurization process, but are difficult to be generalized for various reasons.
In the known method, the prior art needs to be greatly modified in application, even carbon steel materials are corroded, the application cost is high, the chemical stability is poor, and in some desulfurization processes, only the sulfo groups are converted into sulfate radicals, so that the method is difficult to be widely adopted by users.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the HZB salt-inhibiting desulfurizer, which solves the problems mentioned in the background technology.
In order to achieve the purpose, the invention is realized by the following technical scheme: the HZB salt-inhibiting desulfurizer comprises a mixture of monomorpholinodiglycol and dimorpholinodiethylene glycol as main raw materials or a high-boiling product of monomorpholinodiglycol or dimorpholinodiethylene glycol or morpholine;
the main raw material, related organic acid with PK value of more than 2.5 and appropriate participates are fully mixed and reacted to generate the catalytic salt-inhibiting desulfurizer, wherein K is the dissociation constant, and PK is the negative logarithm of K.
The HZB salt-inhibiting desulfurizing agent is preferably one of the related acids such as formic acid, citric acid, propionic acid and benzoic acid.
The HZB salt-suppressing desulfurizing agent as described above, wherein the preferable participants are phthalocyanine cobalt, hydroquinone, anthraquinone disulfonic acid disodium salt, and the like.
Compared with the prior art, the invention has the following beneficial effects: the HZB salt-inhibiting desulfurizer of the invention can completely avoid the generation of thiosulfate and sulfate and thiocyanate, can effectively remove sulfide, has wide application, low cost and stable chemical property, and has an anti-corrosion function on carbon steel equipment.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a technical scheme that: the HZB salt-inhibiting desulfurizer comprises a main raw material, a mixture of monomorpholinodiglycol and dimorpholinodiethylene glycol or one of monomorpholinodiglycol and dimorpholinodiethylene glycol or a morpholine high-boiling substance;
the main raw material is fully mixed with relevant organic acid (the organic acid is one of relevant acids such as formic acid, citric acid, propionic acid, benzoic acid and the like) with PK value of more than 2.5 and appropriate participators (the participators such as cobalt phthalocyanine, hydroquinone, anthraquinone disulfonic acid disodium salt and the like) to react to generate the catalytic salt-inhibiting desulfurizer, and when the catalytic salt-inhibiting desulfurizer is used, the catalytic salt-inhibiting desulfurizer only needs to be added into the existing relevant desulfurization liquid.
Example (b): 20 to 90 percent of main raw material, 10 to 40 percent of organic acid and 0.1 to 20 percent of participator are subjected to combination reaction at the temperature of between 40 and 160 ℃ to generate the catalytic salt-inhibiting desulfurizer.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (3)
- The HZB salt-inhibiting desulfurizer is characterized in that: the high boiling point substance comprises a mixture of a main raw material of monomorpholinyl diethylene glycol and dimorpholinyl diethylene glycol or monomorpholinyl diethylene glycol or dimorpholinyl diethylene glycol or morpholine;the main raw material, related organic acid with PK value of more than 2.5 and appropriate participates are fully mixed and reacted to generate the catalytic salt-inhibiting desulfurizer, K is the dissociation constant, and PK is the negative logarithm of K.
- 2. The HZB salt-suppressing and desulfurizing agent of claim 1, wherein: the organic acid is one of the related acids such as formic acid, citric acid, propionic acid and benzoic acid.
- 3. The HZB salt-suppressing and desulfurizing agent of claim 1, wherein: such as cobalt phthalocyanine, hydroquinone, anthraquinone disulfonate disodium salt, and the like.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010806695.8A CN111905804A (en) | 2020-08-12 | 2020-08-12 | HZB salt-inhibiting desulfurizing agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010806695.8A CN111905804A (en) | 2020-08-12 | 2020-08-12 | HZB salt-inhibiting desulfurizing agent |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111905804A true CN111905804A (en) | 2020-11-10 |
Family
ID=73283928
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010806695.8A Pending CN111905804A (en) | 2020-08-12 | 2020-08-12 | HZB salt-inhibiting desulfurizing agent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111905804A (en) |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE750177A (en) * | 1969-05-20 | 1970-10-16 | Koppers Gmbh Heinrich | PROCESS FOR EXTRACTING COS AND CS2 BY WASHING FROM TECHNICAL GAS |
| EP0140191A2 (en) * | 1983-10-07 | 1985-05-08 | Ford, Bacon & Davis Inc. | Tail gas treating process |
| US4816238A (en) * | 1986-05-01 | 1989-03-28 | The Dow Chemical Company | Method and composition for the removal of hydrogen sulfide from gaseous streams |
| CN1056259A (en) * | 1990-04-28 | 1991-11-20 | 南京化学工业公司研究院 | The method of purification of acidic gas |
| CN1421264A (en) * | 2002-12-11 | 2003-06-04 | 南化集团研究院 | Absorbing liquid for eliminating sulfide from gas mixture |
| CN101327396A (en) * | 2008-07-31 | 2008-12-24 | 深圳市龙澄高科技环保有限公司 | Method and device for removing hydrogen sulfide from gas containing hydrogen sulfide and recovering sulfer using catalytic oxidation |
| WO2010006096A1 (en) * | 2008-07-11 | 2010-01-14 | Smithkline Beecham Corporation | Processes for the preparation of anti-viral compounds and compositions containing them |
| CN102994187A (en) * | 2012-12-11 | 2013-03-27 | 江苏汉光实业股份有限公司 | Selective desulfurizing agent |
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| US20190143262A1 (en) * | 2016-04-25 | 2019-05-16 | Basf Se | Use of morpholine-based hindered amine compounds for selective removal of hydrogen sulfide |
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-
2020
- 2020-08-12 CN CN202010806695.8A patent/CN111905804A/en active Pending
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| EP0140191A2 (en) * | 1983-10-07 | 1985-05-08 | Ford, Bacon & Davis Inc. | Tail gas treating process |
| US4816238A (en) * | 1986-05-01 | 1989-03-28 | The Dow Chemical Company | Method and composition for the removal of hydrogen sulfide from gaseous streams |
| CN1056259A (en) * | 1990-04-28 | 1991-11-20 | 南京化学工业公司研究院 | The method of purification of acidic gas |
| CN1421264A (en) * | 2002-12-11 | 2003-06-04 | 南化集团研究院 | Absorbing liquid for eliminating sulfide from gas mixture |
| WO2010006096A1 (en) * | 2008-07-11 | 2010-01-14 | Smithkline Beecham Corporation | Processes for the preparation of anti-viral compounds and compositions containing them |
| CN101327396A (en) * | 2008-07-31 | 2008-12-24 | 深圳市龙澄高科技环保有限公司 | Method and device for removing hydrogen sulfide from gas containing hydrogen sulfide and recovering sulfer using catalytic oxidation |
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Application publication date: 20201110 |
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