CN106474873B - A method of the absorption and separation ammonia from ammonia-contaminated gas - Google Patents
A method of the absorption and separation ammonia from ammonia-contaminated gas Download PDFInfo
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- CN106474873B CN106474873B CN201611031050.1A CN201611031050A CN106474873B CN 106474873 B CN106474873 B CN 106474873B CN 201611031050 A CN201611031050 A CN 201611031050A CN 106474873 B CN106474873 B CN 106474873B
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- ammonia
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- contaminated gas
- separation
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 255
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 128
- 238000000034 method Methods 0.000 title claims abstract description 38
- 238000010521 absorption reaction Methods 0.000 title claims abstract description 29
- 238000000926 separation method Methods 0.000 title claims abstract description 24
- 239000002250 absorbent Substances 0.000 claims abstract description 45
- 230000002745 absorbent Effects 0.000 claims abstract description 45
- 239000002904 solvent Substances 0.000 claims abstract description 38
- 230000005496 eutectics Effects 0.000 claims abstract description 32
- 238000003795 desorption Methods 0.000 claims abstract description 21
- 239000007788 liquid Substances 0.000 claims abstract description 21
- 150000007513 acids Chemical class 0.000 claims abstract description 10
- -1 salt compounds Chemical class 0.000 claims abstract description 8
- 239000000654 additive Substances 0.000 claims abstract description 7
- 230000000996 additive effect Effects 0.000 claims abstract description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 14
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 12
- 235000011187 glycerol Nutrition 0.000 claims description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 6
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims description 5
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 4
- 230000031709 bromination Effects 0.000 claims description 2
- 238000005893 bromination reaction Methods 0.000 claims description 2
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 238000005660 chlorination reaction Methods 0.000 claims description 2
- 230000002411 adverse Effects 0.000 claims 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims 1
- 238000004064 recycling Methods 0.000 abstract description 20
- 239000007789 gas Substances 0.000 description 42
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 26
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 18
- 238000011084 recovery Methods 0.000 description 17
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 16
- 229910052757 nitrogen Inorganic materials 0.000 description 13
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 10
- 239000001257 hydrogen Substances 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- 150000002431 hydrogen Chemical class 0.000 description 9
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 description 8
- 235000019743 Choline chloride Nutrition 0.000 description 8
- 229910052786 argon Inorganic materials 0.000 description 8
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical compound [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 description 8
- 229960003178 choline chloride Drugs 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 238000009434 installation Methods 0.000 description 4
- 229960004063 propylene glycol Drugs 0.000 description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 230000006837 decompression Effects 0.000 description 3
- 230000007812 deficiency Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 description 3
- 229960001553 phloroglucinol Drugs 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- UFBJCMHMOXMLKC-UHFFFAOYSA-N 2,4-dinitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O UFBJCMHMOXMLKC-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000035800 maturation Effects 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 229940058015 1,3-butylene glycol Drugs 0.000 description 1
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241000406668 Loxodonta cyclotis Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- KOCXMMTWVKMODE-UHFFFAOYSA-N bromobenzene;phosphane Chemical compound P.BrC1=CC=CC=C1 KOCXMMTWVKMODE-UHFFFAOYSA-N 0.000 description 1
- 235000019437 butane-1,3-diol Nutrition 0.000 description 1
- OWBTYPJTUOEWEK-UHFFFAOYSA-N butane-2,3-diol Chemical compound CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 210000000232 gallbladder Anatomy 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 231100001231 less toxic Toxicity 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- 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
- B01D53/14—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 by absorption
- B01D53/1493—Selection of liquid materials for use as absorbents
-
- 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
- B01D53/14—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 by absorption
- B01D53/1418—Recovery of products
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/02—Preparation, purification or separation of ammonia
- C01C1/12—Separation of ammonia from gases and vapours
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
- B01D2252/50—Combinations of absorbents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/40—Nitrogen compounds
- B01D2257/406—Ammonia
Landscapes
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Gas Separation By Absorption (AREA)
- Treating Waste Gases (AREA)
Abstract
The method of the invention discloses a kind of from ammonia-contaminated gas absorption and separation ammonia, includes the following steps: to contact using hydridization eutectic solvent as absorbent with ammonia-contaminated gas, absorption obtains the absorbing liquid containing ammonia, and absorbing liquid obtains ammonia through Desorption separation again；The hydridization eutectic solvent is made of Acidic Compounds, salt compounds and additive three parts.The present invention is using hydridization eutectic solvent as absorbent, and using absorption-desorption method, recycling separation ammonia, the absorbent has very high ammonia solubility and separation selectivity, and ammonia may be implemented efficiently separates recycling.
Description
Technical field
The present invention relates to the separation of ammonia-contaminated gas and recovery purifying field, and in particular to a kind of to utilize hydridization eutectic solvent
The method of absorption and separation ammonia from ammonia-contaminated gas.
Background technique
A large amount of ammonia-contaminated gas is produced in the chemical processes such as Ammonia Production, liquefied ammonia storage and ammonia refrigeration, if directly
Run in and put, not only pollutes atmosphere, endangers human health, but also cause the huge waste of resource.Therefore from synthetic ammonia tailgas etc.
Ammonia is separated and recovered in ammonia-contaminated gas has important practical significance.
Solvent absorption is the common methods that ammonia is separated from ammonia-contaminated gas, and the absorbent of use is mainly water or acid
Aqueous solution.Water absorption method technology maturation, but that there are solvent volatilities is strong, water reuse (treatment process energy consumption is high, discharge of wastewater is more, recovery ammonia
The deficiencies of rate is relatively low.Use the aqueous solution of inorganic acid or organic acid that ammonia recovery can be improved for absorbent, but it is tired to there is desorption
Difficult, the problems such as solvent volatility is strong, corrosivity is strong, ammonium salt product added value is low.Other common methods include low temperature recycling, film point
From, absorption method etc., there are ammonia recoveries it is relatively low, step is more, separation material consumption is big the deficiencies of.
Patent ZL201410413728.7 discloses a kind of technique of Ammonia recovery, and the ammonia of plant emissions enters absorption tower
It is absorbed in tower reactor by deionized water, a small amount of ammonia, water vapour and inert gas can escape into packing material absorbing from deionized water
Section carries out washing absorption again to a small amount of ammonia for entering middle part packing material absorbing section with the deionized water of absorbing ammonia, and containing for evolution is micro-
The water vapour and inert gas for measuring ammonia enter the cooling condensation segment in top, and micro-ammonia is also dissolved in condensate and flows back into tower reactor, most
Inert gas is discharged by demister.
Patent ZL201210164497.1 discloses a kind of recovery method of ammonia-containing exhaust, comprising the following steps: will be described
Ammonia-containing exhaust is condensed, and weak aqua ammonia and condensed ammonia tail gas are obtained；The weak aqua ammonia is distilled, with obtain ammonia,
Liquid after water and distillation；The first spray-absorption is carried out to the condensed ammonia tail gas and the ammonia with ammonia nitrogen water is washed, to obtain
First spray ammonia nitrogen solution and the first spray residual ammonia tail gas, wherein the ammonia nitrogen concentration in the ammonia nitrogen solution is not less than 70g/L.
Patent CN201510039431.3 is using the refrigerant nitrogen drawn in liquefaction separation ice chest in 2.5-4.5MPa
Operating pressure under synthetic ammonia tailgas is cooled to -5 DEG C, so that the ammonia in synthetic ammonia tailgas is cooled to liquefied ammonia, carry out gas-liquid point
From obtaining liquefied ammonia product and separate the synthetic ammonia tailgas after liquefied ammonia, then the liquefied ammonia product and synthetic ammonia tailgas heat exchange be extremely
Ammonia product is made in liquefied ammonia boiling, and the synthetic ammonia tailgas after the separation liquefied ammonia removes ammonia through washing depth again, and by-product obtains ammonia
Water, washing depth is except ammonia content≤100ppm in the synthetic ammonia tailgas after ammonia.
Patent ZL201310699052.8 discloses a kind of method of recycling ammonia from synthesis ammonia relief gas, including locates in advance
Reason process, membrane separating process and ammonia recovering process.Using first can be resistant to for a long time at resistant to ammonia film of the ammonia phase concentration less than 6%
Reason synthesis ammonia relief gas, recycles hydrogen therein and most of ammonia, then using the method for washing and ammonia still process, recycles UF membrane
The ammonia contained in gas is retained afterwards, is changed into liquefied ammonia product.
Summary of the invention
The present invention provides a kind of method using hydridization eutectic solvent absorption and separation ammonia from ammonia-contaminated gas, with hydridization
Eutectic solvent makees absorbent, and using absorption-desorption method, recycling separation ammonia, the absorbent has very high ammonia
Gas solubility and separation selectivity, ammonia may be implemented efficiently separates recycling.
A method of the absorption and separation ammonia from ammonia-contaminated gas includes the following steps:
It using hydridization eutectic solvent as absorbent, is contacted with ammonia-contaminated gas, absorption obtains the absorbing liquid containing ammonia, absorbs
Liquid obtains ammonia through Desorption separation again；The hydridization eutectic solvent is by Acidic Compounds, salt compounds and additive three
Part forms.
The ammonia-contaminated gas is the gaseous mixture of the process equipments such as synthetic ammonia installation, ammonia refrigerating installation discharge, is mainly contained
Nitrogen, hydrogen, methane, ammonia, argon gas etc..The residual exhaust obtained after absorbent absorbs is hydrogen, nitrogen, methane, argon gas
Equal gases.
Solvent absorption recycling ammonia has many advantages, such as that technology maturation, device are simple, and critical issue is absorbent
Design.When recycling the ammonia in ammonia-contaminated gas with selected absorbent, absorbent must have good solvability to ammonia
And selectivity, and there is very low volatility.And absorbent should have good Environmental compatibility and more cheap
Preparation cost.
The present invention makees absorbent with hydridization eutectic solvent, and using absorption-desorption method, recycling separation ammonia is described
Absorbent have very high ammonia solubility and separation selectivity, ammonia may be implemented efficiently separates recycling.
Eutectic solvent be mixed in a certain ratio by two or more substance after formed show with eutectic
The liquid of elephant, has the characteristics that almost non-volatile, therefore volatile conventional absorbents, difficult life, pollution can be overcome big
The deficiencies of.Meanwhile compared with ionic liquid, with preparation process, simple, raw material is easy to get, is at low cost, is degradable eutectic solvent
The advantages that property is good.But conventional eutectic solvent or weaker with the compatibility of ammonia, lead to that ammonia solubility is low, the rate of recovery
It is low；Structure in solvent is destroyed by amino molecule after contacting with ammonia, and solvent gradually becomes solid-state from liquid, leads to absorption process
It is obstructed interruption, can not carry out, and solvent is difficult to recycle.
Different from conventional eutectic solvent, hydridization eutectic solvent of the present invention is Acidic Compounds, salt
The organic whole that three kinds of components of compound and additive are formed under non-binding effect driving, can not only be simultaneously and in amino molecule
Nitrogen, hydrogen atom occur compared with strong interaction, and its structure and phase before it is absorbed after can remain unchanged, to obtain very high
Ammonia solubility, selective and good solvent cycle performance.
In the present invention preferably, the hydridization eutectic solvent is by Acidic Compounds A, salt compounds B and addition
Agent C three parts composition；The molar ratio of the Acidic Compounds, salt compounds and additive is (1~5): 1:(1~5), into
One step is preferably (2~5): 1:(2~5).
Preferably, the Acidic Compounds A is one of phenol, fortified phenol, benzenediol, benzenetriol；
Preferably, the salt compounds B is one of quaternary ammonium chloride or bromination quaternary alkylphosphonium salt；
Preferably, the addition of C is one of ethylene glycol, propylene glycol, glycerine, butanediol.
It is further preferred that the Acidic Compounds A is one of fortified phenol, benzenediol, benzenetriol, the salt
Class compound B is one of choline chloride, tetrabutylammonium chloride.
Still more preferably, the hydridization eutectic solvent is one of following combination: benzenediol/choline chloride/
Ethylene glycol, benzenediol/choline chloride/glycerine, benzenetriol/choline chloride/glycerine, benzenetriol/tetrabutylammonium chloride/1,2-
Propylene glycol, 2,4- dinitrophenol/tetrabutylammonium chloride/1,4- butanediol.
When selecting any of the above-described combination, to the rate of recovery of ammonia in ammonia-contaminated gas 92% or more.
Still further preferably, the hydridization eutectic solvent is one of following combination: hydroquinone/chlorination gallbladder
Alkali/ethylene glycol (molar ratio 3:1:3), resorcinol/choline chloride/glycerine (molar ratio 3:1:5), the phloroglucin/tetrabutyl
Ammonium chloride/1,2- propylene glycol (molar ratio 2:1:4).They have good solvability to ammonia, to the rate of recovery of ammonia
Up to 99% or more.
Preferably, the reaction condition when absorbent and ammonia-contaminated gas contact are as follows: temperature is 10~50 DEG C, and pressure is
1.0~5.0MPa.
Preferably, absorbent contacts the condition for absorbing ammonia with ammonia-contaminated gas are as follows: temperature is 10~50 DEG C, and pressure is
1.0~5.0MPa；It is further preferred: absorb temperature be 20 DEG C, absorption pressure 2.0MPa.Research shows that temperature is too low, it is low total
The mobility of molten solvent is deteriorated, and process energy consumption becomes larger；The solubility of the excessively high then ammonia of temperature declines.Higher absorption pressure is advantageous
In Ammonia recovery.
Desorption separation can be used heating desorption, can also heat up, depressurize and with desorb；Preferably, the desorption point
From condition are as follows: temperature is 50~80 DEG C, and pressure is 0.05~1.0MPa；Further preferably are as follows: desorption temperature is 65 DEG C, solves suction pressure
Power is 0.2MPa.
The specific steps using hydridization eutectic solvent method of absorption and separation ammonia from ammonia-contaminated gas are as follows: will
Absorbent is cooled to 10~50 DEG C, contacts in the case where pressure is 1.0~5.0MPa with ammonia-contaminated gas, absorption obtains the absorption containing ammonia
Liquid, then ammonia is obtained through Desorption separation, desorption temperature is 50~80 DEG C, and desorption pressures are 0.1~1.0MPa.
Preferably, the way of contact of the absorbent and ammonia-contaminated gas is counter current contacting, biography can be preferably improved
Matter effect.
Compared with prior art, the invention has the following beneficial effects:
1. hydridization eutectic solvent synthetic method is simple, raw material are easy to get, and less toxic low pollution, as absorbent, it has
Good thermal stability and extremely low saturated vapor pressure can realize repeatedly recycling by heating under reduced pressure, and in gas
Absorbent steam will not be generated in desorption and product is polluted.
2. hydridization eutectic solvent designed by the present invention not only has very strong amino molecule compatibility and Selective recognition
Ability, and its structure and phase remain unchanged afterwards before it is absorbed, to realize the efficient removal and recycling of ammonia.
3. the method for the present invention using hydridization eutectic solvent as absorbent, using absorption-desorption method, recycles ammonia-contaminated gas
In ammonia, and the continuous recycling of hydridization eutectic solvent may be implemented, has that separative efficiency is high, low energy consumption, safety collar
It protects, be suitable for the advantages that industrialized production.
Specific embodiment
In the present invention such as using the specific steps of hydridization eutectic solvent method of absorption and separation ammonia from ammonia-contaminated gas
Under:
1, ammonia-contaminated gas pressure is adjusted to 1.0MPa~5.0MPa, is passed through from the bottom on absorption tower, it will be cooled to 10~
50 DEG C of absorbent is added from the tower top on absorption tower, and tower bottom obtains the absorbing liquid rich in ammonia, and tower top is obtained rich in hydrogen, nitrogen
The residual exhaust of the gases such as gas, methane, argon gas.
2, the absorbing liquid rich in ammonia enters desorber from below, and using the method for heating desorption, desorption temperature control exists
50~80 DEG C, or using heating, decompression and with desorbing, pressure limit is 0.05~1.0MPa, and tower top obtains ammonia, and tower bottom obtains
Absorbent, and can be used for recycling.
Embodiment 1
Absorbent is that the hydridization eutectic that hydroquinone/choline chloride/ethylene glycol (molar ratio 3:1:3) mixes is molten
Agent.Synthetic ammonia tailgas forms (percentage by volume): hydrogen 51.8%, nitrogen 19.3%, ammonia 6.5%, argon gas 3.6%, methane
18.8%.Synthetic ammonia tailgas is passed through at 3.8MPa from absorbing tower bottom, and absorbent is added in absorption tower tower top, and absorbent is at 30 DEG C
Lower and synthetic ammonia tailgas counter current contacting absorbs, it is ensured that the ammonia of wherein most is absorbed, and tower bottom obtains the absorption rich in ammonia
Liquid, tower top obtain the residual exhausts such as the nitrogen, hydrogen, methane of slightly solubility.
Tower bottom absorbing liquid enters desorber, and using the method for heating desorption, desorption temperature control is in 70 DEG C, pressure
0.3MPa, tower top obtain ammonia, and tower bottom is absorbed agent, recycling.Ammonia recovery rate is up to 99.6%.
Embodiment 2
Absorbent is that the hydridization eutectic that resorcinol/choline chloride/glycerine (molar ratio 3:1:5) mixes is molten
Agent.Synthetic ammonia tailgas composition: hydrogen 59.5%, nitrogen 22.3%, ammonia 5.3%, argon gas 3.8%, methane 9.1%.As implemented
Example 1, counter current contacting absorbs at 20 DEG C, 4.0MPa with absorbent, and absorbing liquid desorbs ammonia, tower bottom at 65 DEG C, 0.2MPa
The agent that is absorbed recycling.Ammonia recovery rate is up to 99.1%.
Embodiment 3
Absorbent is that the hydridization that phloroglucin/tetrabutylammonium chloride/1,2- propylene glycol (molar ratio 2:1:4) mixes is low
Congruent melting solvent.Synthetic ammonia tailgas composition: hydrogen 56.1%, nitrogen 20.5%, ammonia 3.9%, argon gas 4.7%, methane 14.8%.
Such as embodiment 1, counter current contacting absorbs at 20 DEG C, 3.5MPa with absorbent, and absorbing liquid heats up decompression at 65 DEG C, 0.08MPa
Desorb ammonia, tower bottom is absorbed agent recycling.Ammonia recovery rate is up to 99.5%.
Embodiment 4
Absorbent is that 2,4- dinitrophenol/tetrabutylammonium chloride/1,4- butanediol (molar ratio 1:1:2) mixes
Hydridization eutectic solvent.Synthetic ammonia tailgas composition: hydrogen 62.2%, nitrogen 21.4%, ammonia 1.9%, argon gas 5.0%, methane
9.5%.Such as embodiment 1, counter current contacting absorbs at 10 DEG C, 4.5MPa with absorbent, and absorbing liquid heats up at 70 DEG C, 0.1MPa
Decompression desorbs ammonia, and tower bottom is absorbed agent recycling.Ammonia recovery rate is up to 92.8%.
Embodiment 5
Absorbent is that the hydridization eutectic that phloroglucin/choline chloride/glycerine (molar ratio 2:1:3) mixes is molten
Agent.Such as embodiment 1, purified synthesis gas workshop section ammonia refrigerating installation exhaust gas (wherein ammonia level 66.9%, other are mainly nitrogen)
Counter current contacting absorbs at 40 DEG C, 2.0MPa with absorbent, and absorbing liquid desorbs ammonia in 60 DEG C of heatings, and tower bottom is absorbed agent
Recycling.Ammonia recovery rate is up to 94.5%.
Embodiment 6
Absorbent is the hydridization eutectic that phenol/etamon chloride/1,3 butylene glycol (molar ratio 2:1:3) mixes
Solvent.Synthetic ammonia tailgas composition: hydrogen 65.1%, nitrogen 19.1%, ammonia 2.5%, argon gas 2.4%, methane 10.9%.Strictly according to the facts
Example 1 is applied, counter current contacting absorbs at 15 DEG C, 2.5MPa with absorbent, and absorbing liquid heats up at 75 DEG C and desorbs ammonia, and tower bottom obtains
It is recycled to absorbent.Ammonia recovery rate is up to 90.9%.
Embodiment 7
Absorbent mixes miscellaneous for three phenyl-bromide Phosphonium of 4- chlorophenol/first base/2,3- butanediol (molar ratio 3:1:5)
Change eutectic solvent.Such as embodiment 1, purified synthesis gas workshop section ammonia refrigerating installation exhaust gas (wherein ammonia level 72.3%, other masters
To be nitrogen) and absorbent counter current contacting absorption at 30 DEG C, 2.0MPa, absorbing liquid heats up at 70 DEG C, 0.3MPa depressurizes solution
Be sucked out ammonia, tower bottom be absorbed agent recycling.Ammonia recovery rate is up to 91.3%.
The foregoing is merely the specific implementation cases of the invention patent, but the technical characteristic of the invention patent is not limited to
This, within the field of the present invention, made changes or modifications all cover of the invention special any those skilled in the relevant art
Among sharp range.
Claims (6)
1. a kind of method of the absorption and separation ammonia from ammonia-contaminated gas, feature is as follows, includes the following steps:
It using hydridization eutectic solvent as absorbent, is contacted with ammonia-contaminated gas, absorption obtains the absorbing liquid containing ammonia, and absorbing liquid passes through again
Desorption separation obtains ammonia；The hydridization eutectic solvent is by Acidic Compounds, salt compounds and additive three parts group
At；The Acidic Compounds are one of phenol, fortified phenol, benzenediol, benzenetriol；The salt compounds are chlorination
One of quaternary ammonium salt or bromination quaternary alkylphosphonium salt；The additive is one of ethylene glycol, propylene glycol, glycerine and butanediol.
2. method according to claim 1, which is characterized in that the Acidic Compounds, salt compounds and additive
Molar ratio is (1~5): 1:(1~5).
3. method according to claim 1, which is characterized in that the reaction condition when absorbent and ammonia-contaminated gas contact
Are as follows: temperature is 10~50 DEG C, and pressure is 1.0~5.0MPa.
4. method according to claim 1, which is characterized in that the condition of the desorption are as follows: 50~80 DEG C of temperature, pressure 0.1
~1.0MPa.
5. method according to claim 1, which is characterized in that the ammonia-contaminated gas be cooled to after 10~50 DEG C again with absorbent
Contact.
6. method according to claim 1, which is characterized in that the way of contact of the absorbent and ammonia-contaminated gas is that adverse current connects
Touching.
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| US10793801B2 (en) | 2017-02-06 | 2020-10-06 | Exxonmobil Chemical Patents Inc. | Low transition temperature mixtures and lubricating oils containing the same |
| CN107899371B (en) * | 2017-12-27 | 2021-02-02 | 中国科学院过程工程研究所 | Method for efficiently and reversibly absorbing ammonia gas by using ionic eutectic solvent |
| CN108452640B (en) * | 2018-04-10 | 2021-01-19 | 南昌大学 | Ternary eutectic solvent |
| CN109260896B (en) * | 2018-11-30 | 2021-02-26 | 浙江工业大学 | Ammonium thiocyanate eutectic solvent for absorbing ammonia gas and ammonia gas adsorption method |
| CN110180329B (en) * | 2019-06-25 | 2022-02-25 | 中国石油大学(华东) | Novel benzene series volatile organic compound absorbent, preparation method and application thereof |
| CN112717633A (en) * | 2019-10-28 | 2021-04-30 | 中国石油化工股份有限公司 | Treatment method of chlorine-containing volatile organic compound waste gas |
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