CN106823689A - A kind of method for purifying amine liquid in organic amine doctor treatment - Google Patents
A kind of method for purifying amine liquid in organic amine doctor treatment Download PDFInfo
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- CN106823689A CN106823689A CN201611227166.2A CN201611227166A CN106823689A CN 106823689 A CN106823689 A CN 106823689A CN 201611227166 A CN201611227166 A CN 201611227166A CN 106823689 A CN106823689 A CN 106823689A
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- Prior art keywords
- organic amine
- amine
- doctor treatment
- liquid
- salt
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- 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
- B01D53/1456—Removing acid 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
- B01D53/14—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
- B01D53/1425—Regeneration of liquid absorbents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
-
- 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
- B01D2252/20—Organic absorbents
- B01D2252/204—Amines
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/30—Sulfur compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/42—Ion-exchange membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/48—Antimicrobial properties
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a kind of method for purifying amine liquid in organic amine doctor treatment, separated during saliferous amine liquid in organic amine doctor treatment is delivered into membrane separator by liquid pushing tube using pump;Contain the organic amine and 1 ~ 25% salt that mass fraction is 0.01 ~ 5% in saliferous amine liquid in the organic amine doctor treatment.The UF membrane relevant device that the present invention is used can be used without regeneration, there is no unnecessary waste water to produce during whole amine purification is domestic, the recycling enough steady in a long-term in the entire system of organic amine liquid energy, significantly reduce the overall operation cost of desulphurization system, and entirely produce it is domestic in do not produce " three wastes ", production environment is good, improves the yield of product and the quality of product, is preferable environmental protection technique.
Description
Technical field
The present invention relates to separation technology field, the purification method of amine liquid in more particularly to a kind of organic amine doctor treatment.
Background technology
At present, amine process desulfurization technology is commonly used in thermal power generation corporations of China, in early days using MEA, DEA and DIPA
Desulfurization, it is now to use diamine such as mainly based on introduction more:HEEDA, HEP, DABCD, BHEP and HPP(N, N- bis-(2- hydroxyls
Propyl group)Piperazine)Deng.Under the conditions of suitable gas liquid ratio, plus a small amount of additive MDEA and MEA mixing alkanolamine solution, with very
Selectivity well and very high desulfurization efficiency, can make the desulfurization degree in unstripped gas reach more than 98%.
Typical organic amine flue gas desulfurization is broadly divided into 4 processes, the i.e. pre-separation of flue gas, SO2Absorption, SO2Regeneration
With the purification of amine liquid.
(1)The pre-separation of flue gas:Flue gas chilling and saturation in Water spray pre-scrubber, while removing little particle ash
Dirt and most of strong acid, the low sour environment of cleaning solution pH value, prevents SO in pre-scrubber2Hydrolysis and make it with gas phase
Into absorption tower.
(2)SO2Absorption:Absorbent is in contact with flue gas in absorption plant, absorbent and SO2Generation invertibity is reacted.
It is general using multistage reflux formula contact device form, or spray-absorption device form in order to reach the assimilation effect of maximum.Only
Flue gas after change meets environmental protection standard and sends flue emptying back to.
(3)SO2Regeneration:Regenerating unit includes a heat exchanger, will absorb SO2Absorbent it is logical from absorption plant
Enter regenerating unit after over-heat-exchanger reduction temperature.Absorbent flows through regenerating unit, SO from the top down2Separated from absorbent
Out, the SO for separating2Steam enters one condenser of people, in condenser, after most of steam is condensed, returns to regeneration
Device.The gaseous state SO of saturation2By a blower fan or compressor, regeneration is separated, be sent to acid making system.The absorbent of regeneration turns into
Weak base amine pumps into absorption plant through boiler economizer, heat exchanger and a reactive tank.
(4)The purification of amine liquid:Ion in amine liquid is sloughed by ion exchange column, the organic amine after purification enter absorption tower after
Continuous desulfurization.
Problem present in current organic amine purification technique:Ion in amine liquid is sloughed by ion exchange column, due to
The exchange capacity of resin is limited in ion exchange column, and treatment is accomplished by being regenerated with chemical agent to a certain extent afterwards, its mistake
Journey can produce a large amount of dark color waste water again while chemicals is consumed with the energy, cause secondary environmental pollution, and be difficult to control
Reason.In addition, in actual motion due to organic amine liquid in containing impurity it is more, ion exchange column clogging often occurs,
The purification of amine liquid is severely impacted, can not be circulated steadily in the long term in the entire system which results in organic amine liquid makes
With.
The content of the invention
Can realize being produced without unnecessary waste water the present invention solves the technical problem of providing a kind of simple and easy to do, economical
Organic amine doctor treatment in amine liquid purification method.
In order to solve the above technical problems, one aspect of the present invention is:
A kind of method for purifying amine liquid in organic amine doctor treatment is provided, by saliferous amine liquid in organic amine doctor treatment using pump by sending
Liquid pipe is separated in delivering to membrane separator;In saliferous amine liquid in the organic amine doctor treatment containing mass fraction be 0.01 ~
5% organic amine and 1 ~ 25% salt.
In a preferred embodiment of the present invention, anions and canons exchange membrane is installed in the membrane separator, it is described it is cloudy,
Cation-exchange membrane is different with the permeability of salt to organic amine.
In a preferred embodiment of the present invention, the membrane separator includes amberplex group, the amberplex
Group is made up of cation-exchange membrane, dividing plate and anion-exchange membrane.
In a preferred embodiment of the present invention, the dividing plate is anti-corrosive rubber.
In a preferred embodiment of the present invention, the electrode that electrode is placed through on the ion exchange module side is spacing
Hole.
In a preferred embodiment of the present invention, the anti-ion deposition of antibacterial is also covered with outside the amberplex group to apply
Layer.
In a preferred embodiment of the present invention, the salt is inorganic salts and organic amine salt.
In a preferred embodiment of the present invention, the temperature of saliferous amine liquid is 0 ~ 50 DEG C in the organic amine doctor treatment.
The beneficial effects of the invention are as follows:A kind of method for purifying amine liquid in organic amine doctor treatment of the present invention, the film point of use
Be can be used without regeneration from relevant device, there is no unnecessary waste water to produce during whole amine purification is domestic, organic amine liquid energy is reached
Recycling steady in a long-term in the entire system, significantly reduces the overall operation cost of desulphurization system, and entirely produces
Do not produced in domestic " three wastes ", production environment is good, improves the yield of product and the quality of product, is preferable environmental protection
Technique.
Specific embodiment
Presently preferred embodiments of the present invention is described in detail below so that advantages and features of the invention can be easier to by
It will be appreciated by those skilled in the art that apparent clearly being defined so as to be made to protection scope of the present invention.
Embodiment 1:The organic amine and 25% sulphur that mass fraction is 2% will be contained in amine liquid containing salt in organic amine doctor treatment
The 5000g solution of sour sodium, at a temperature of 20 DEG C, using pump by liquid pushing tube, in delivering to the membrane separator of built-in zwitterion film,
Because the conductance to organic amine with salt in the solution is different, zwitterion film is different with salt permeability to organic amine, so that can
Appropriate water is added to act synergistically to separate organic amine and salt, in membrane separator, final process obtains 4600g and is containing organic amine
1.7%th, the solution of sodium sulphate 0.1%(Mass fraction).
Embodiment 2:The organic amine and 20% sulphur that mass fraction is 5% will be contained in amine liquid containing salt in organic amine doctor treatment
The 5000g solution of sour sodium, at a temperature of 40 DEG C, using pump by liquid pushing tube, in delivering to the membrane separator of built-in zwitterion film,
Because the conductance to organic amine with salt in the solution is different, zwitterion film is different with salt permeability to organic amine, so that can
Appropriate water is added to act synergistically to separate organic amine and salt, in membrane separator, final process obtains 4500g and is containing organic amine
4.9%th, the solution of sodium sulphate 0.2%(Mass fraction).
Embodiment 3:To have with 15% containing the organic amine that mass fraction is 5% in amine liquid containing salt in organic amine doctor treatment
The 5000g solution of machine amine salt, at a temperature of 10 DEG C, using pump by liquid pushing tube, delivers to the membrane separator of built-in zwitterion film
In, because the conductance to organic amine with salt in the solution is different, zwitterion film is different with salt permeability to organic amine, so that
Organic amine and salt can be separated, adds appropriate water to act synergistically in membrane separator, final process obtains 4900g and is containing organic amine
4.8%th, the solution of organic amine salt 0.23%(Mass fraction).
Embodiment 4:To have with 25% containing the organic amine that mass fraction is 5% in amine liquid containing salt in organic amine doctor treatment
The 5000g solution of machine amine salt, at a temperature of 10 DEG C, using pump by liquid pushing tube, delivers to the membrane separator of built-in zwitterion film
In, because the conductance to organic amine with salt in the solution is different, zwitterion film is different with salt permeability to organic amine, so that
Organic amine and salt can be separated, adds appropriate water to act synergistically in membrane separator, final process obtains 4900g and is containing organic amine
4.8%th, the solution of organic amine salt 0.23%(Mass fraction).
Embodiment 5:To have with 15% containing the organic amine that mass fraction is 5% in amine liquid containing salt in organic amine doctor treatment
The 5000g solution of machine amine salt and 2% sodium sulphate, at a temperature of 10 DEG C, using pump by liquid pushing tube, delivers to built-in zwitterion film
Membrane separator in, because the conductance to organic amine with salt in the solution is different, zwitterion film is penetrating to organic amine and salt
Property it is different, add appropriate water to act synergistically such that it is able to separate organic amine and salt, in membrane separator, final process is obtained
4900g is containing the solution that organic amine is 4.8%, organic amine salt 0.23% and sodium sulphate 0.5%(Mass fraction).
Membrane separator in any of the above-described embodiment, including amberplex group, the amberplex group be by sun from
Proton exchange, dividing plate and anion-exchange membrane composition, anions and canons exchange membrane are different with the permeability of salt to organic amine, every
Plate is made of anti-corrosive rubber, and the electrode in membrane separator is placed through the electrode spacing hole on ion exchange module side,
And the anti-ion deposition coating of antibacterial is also covered with outside amberplex group.The membrane separator, is prevented from impurity in ion
Exchange membrane surface deposition causes the resistance to increase, reduce the effective area of amberplex, maintain membrane separator it is long-term, efficiently,
The working condition of stabilization.
Embodiments of the invention are the foregoing is only, the scope of the claims of the invention is not thereby limited, it is every to utilize this hair
Equivalent structure or equivalent flow conversion that bright description is made, or directly or indirectly it is used in other related technology necks
Domain, is included within the scope of the present invention.
Claims (8)
1. it is a kind of purify organic amine doctor treatment in amine liquid method, it is characterised in that by organic amine doctor treatment saliferous amine liquid profit
Separated in delivering to membrane separator by liquid pushing tube with pump;Contain quality point in saliferous amine liquid in the organic amine doctor treatment
Number is 0.01 ~ 5% organic amine and 1 ~ 25% salt.
2. it is according to claim 1 purification organic amine doctor treatment in amine liquid method, it is characterised in that the membrane separator
In anions and canons exchange membrane is installed, the anions and canons exchange membrane is different with the permeability of salt to organic amine.
3. it is according to claim 2 purification organic amine doctor treatment in amine liquid method, it is characterised in that the membrane separator
Including amberplex group, the amberplex group is made up of cation-exchange membrane, dividing plate and anion-exchange membrane.
4. in purification organic amine doctor treatment according to claim 3 amine liquid method, it is characterised in that the dividing plate is for resistance to
Corrosion rubber.
5. it is according to claim 3 purification organic amine doctor treatment in amine liquid method, it is characterised in that electrode is placed through
Electrode spacing hole on the ion exchange module side.
6. it is according to claim 3 purification organic amine doctor treatment in amine liquid method, it is characterised in that the ion hand over
Change and the anti-ion deposition coating of antibacterial is also covered with outside film group.
7. it is according to claim 1 purification organic amine doctor treatment in amine liquid method, it is characterised in that the salt is nothing
Machine salt and organic amine salt.
8. it is according to claim 1 purification organic amine doctor treatment in amine liquid method, it is characterised in that the organic amine take off
The temperature of saliferous amine liquid is 0 ~ 50 DEG C in sulphur method.
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CN201611227166.2A CN106823689A (en) | 2016-12-27 | 2016-12-27 | A kind of method for purifying amine liquid in organic amine doctor treatment |
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CN201611227166.2A CN106823689A (en) | 2016-12-27 | 2016-12-27 | A kind of method for purifying amine liquid in organic amine doctor treatment |
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CN201611227166.2A Pending CN106823689A (en) | 2016-12-27 | 2016-12-27 | A kind of method for purifying amine liquid in organic amine doctor treatment |
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Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN201880432U (en) * | 2010-07-27 | 2011-06-29 | 赵学法 | Device for removing heat-stable salt in desulfurization amine liquid by membrane method |
CN105084466A (en) * | 2015-09-15 | 2015-11-25 | 江苏久吾高科技股份有限公司 | Sulfurous gas desulfurizer purification technique and device |
-
2016
- 2016-12-27 CN CN201611227166.2A patent/CN106823689A/en active Pending
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN201880432U (en) * | 2010-07-27 | 2011-06-29 | 赵学法 | Device for removing heat-stable salt in desulfurization amine liquid by membrane method |
CN105084466A (en) * | 2015-09-15 | 2015-11-25 | 江苏久吾高科技股份有限公司 | Sulfurous gas desulfurizer purification technique and device |
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