CN106310879A - Method for treating exhaust gas containing ethylene oxide and propylene oxide - Google Patents
Method for treating exhaust gas containing ethylene oxide and propylene oxide Download PDFInfo
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- CN106310879A CN106310879A CN201610877129.XA CN201610877129A CN106310879A CN 106310879 A CN106310879 A CN 106310879A CN 201610877129 A CN201610877129 A CN 201610877129A CN 106310879 A CN106310879 A CN 106310879A
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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
- B01D53/1406—Multiple stage absorption
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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
- B01D53/1418—Recovery of products
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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
- B01D53/1425—Regeneration of liquid absorbents
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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
- B01D53/1487—Removing organic compounds
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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
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/702—Hydrocarbons
- B01D2257/7022—Aliphatic hydrocarbons
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Abstract
The invention relates to a method for treating exhaust gas containing ethylene oxide and propylene oxide. The method is mainly used for solving problems in the prior art that the consumption of washing water is high and washed wastewater is hard to treat. The technical scheme of the invention is as follows: the method for treating the exhaust gas containing the ethylene oxide and the propylene oxide comprises the steps: the exhaust gas enters a first exhaust gas absorption tower and is in contact with first washing water, exhaust gas is exhausted from the top of the tower, enters a second exhaust gas absorption tower and is continuously in contact with second washing water, and exhaust gas is exhausted to atmosphere from the top of the second exhaust gas absorption tower; a washing rich solution of the bottom of the first exhaust gas absorption tower enters a first hydration reactor for a catalytic hydration reaction, and wastewater passes through a lithium bromide refrigerator after the catalytic reaction and then enters the first exhaust gas absorption tower as the first washing water; a washing rich solution of the bottom of the second exhaust gas absorption tower enters a second hydration reactor for a catalytic hydration reaction, and wastewater passes through the lithium bromide refrigerator after the catalytic reaction and then enters the second exhaust gas absorption tower. Through adopting the technical scheme, the problems are solved in a relatively good manner; the method can be used for treating the exhaust gas containing the ethylene oxide and the propylene oxide.
Description
Technical field
The present invention relates to a kind of containing oxirane with the waste gas processing method of expoxy propane.
Background technology
With national society's rapid economic development, country's raising further to environmental requirement.Along with every environmental regulation
Appearance, " people-oriented, environmental protection " is the only way which must be passed of Issues and Crucial Practices of Contemporary Enterprises and social development.
How the processing tail gas of economical rationality is an important directions of environmental protection, meet the energy resource structure of China with
Development strategy.The present invention relates to a kind of to the processing method containing oxirane (EO)/expoxy propane (PO) waste gas, mainly solve with
There is ethylene oxide/propylene oxide washing in technology insufficient, washing consumes big, and washes containing ethylene oxide/propylene oxide
Wash the problems such as waste water difficult treatment.According to " GB 31571-2015 petro chemical industry pollutant emission standard " requirement, in waste gas
The limit value of oxirane and expoxy propane is respectively 0.5,1mg/m3, existing technology is extremely difficult to this requirement, or can be formed
Secondary pollution.Such as, East China University of Science " http://www.docin.com/p-869252916.html " is disclosed uses sulfur
The method of acid-catalyzed hydration, using aqueous solution of ethylene oxide add 0.5～1.0% dilute sulfuric acid as catalyst, at 50～70 DEG C,
Under 9.8～19.6KPa reaction conditions, reaction generates ethylene glycol, and product need to neutralize with alkali liquor.This reaction needs to use sulphuric acid
Although being hydrated by obvious catalytic action with sodium hydroxide acid-base pair EO, but inorganic acid catalyst can causing carbon steel equipment corrosion, and
Inorganic base catalyst can produce some by-products.In washings, introduce inorganic salt simultaneously, generate brine waste, to follow-up waste water
Process the difficulty height of operation, power consumption greatly, do not meet the environmental requirement of economical rationality.
Physical Absorption method: will introduce in absorbing liquid and purify by oxirane waste gas, by after saturated for absorbing liquid through heating,
Resolve, condensation, reclaim；It is relatively big that this law is applicable to its amount, and waste gas component is single, and concentration is low, the gas that temperature is low, but needs configuration
Adding Thermal desorption retracting device, equipment volume is the biggest, invests higher, and oxirane character is active, the follow-up place of absorbing liquid
Reason difficulty.Owing to oxirane is a kind of hazardous chemical component, in addition to there is high toxicity, also there is height inflammability, can be certainly
Dynamic decomposition is also reacted with multiple compounds (including self), and these reactions are generally of strong exothermicity.Owing to having this
, had there is repeatedly major accident in EO/EG and EO derived product process industry in a little characteristics.
It is the most miscible that EO can meet water, and the mid-term from oxirane/aqueous mixtures has (with under atmospheric pressure) in atmosphere
There is inflammability, unless EO to be carried out more than 22 times dilutions (according to volume).In closed system, such as gutter, it may be necessary to dilute
The multiple released is 100 times, the most just can form the mixture not supporting burning.As used water absorption method to process in tail gas
EO/PO, for meeting safety requirements, very big to the consumption demand of washings, cause energy loss.Meanwhile, EO is as active chemistry
Agent, its aqueous solution enters drainage, may carry out reacting (acids, some amine, alkali with other materials in drainage
Metal hydroxides, is in solid such as bleaching clay and the rust etc. of superfine state).Cause danger.Meanwhile, EO and aqueous solution thereof are made
For good antibacterial, biochemical pond and strain may be impacted.
Absorption method: owing to activated carbon is non-polar adsorbent, and oxirane is nonpolar organic compound, so epoxy
Ethane is easily tightly held by activated carbon.The most active charcoal of oxirane adsorbs, and can reach the purifying rate of more than 95%, and equipment is simple,
Invest little, but activated carbon is changed frequently relatively, adds handling, transport, the working procedure such as replacing, and the activity containing oxirane
Carbon subsequent treatment difficulty, causes operating cost to increase, and economy is not good enough.
Direct hydration method: it is legal that direct hydration method is also referred to as oxirane pressure (hydraulic) water.By water and oxirane with mol ratio it is
The solution of 22:1, in shell and tube reactor, with operating condition 150～200 DEG C, is hydrated under conditions of 1.5～2.5MPa
Reaction generates EG, by-product DEG, TEG etc..The method reaction condition is relative complex, and energy consumption is big.Do not meet economical rationality, energy-conservation
The requirement of environmental protection.
Catalytic hydration: for using simple acid base catalysator to corrode, contaminated equipment, also can generate some other pair
Product.And the energy consumption of direct hydration method is the highest, catalytic hydration is used to process the waste liquid Han ethylene oxide/propylene oxide herein, as
The method of a kind of producing glycol by virtue of hydration of ethylene oxide proposed in patent CN201010147789.Can be at low temperature, lower pressure
Under, ethylene oxide/propylene oxide generates ethylene glycol/propylene glycol under catalyst action.By-product is DEG/DPG etc..Reaction is produced
Thing and by-product are safe and reliable, have no side effect, without Fire risk analysis.Due to product and by-product pair in waste liquid
EO/PO has good assimilation effect, and after reaction, waste liquid is capable of circulation changes utilization.It is high that the method has washings utilization rate, energy consumption
Low, after washing, waste liquid is disposable, the feature of plant running safety and stability.
Product ethylene glycol recoverable, ethylene glycol can be used for polyester resin, including fiber, thin film and engineering plastics
Production, can be directly used as coolant and antifreezing agent, the most also be to produce alkyd resin, plasticizer, paint, adhesive, surface
The requisite materials of product such as activating agent, explosive and capacitor electrolyte, are a kind of very important aliphatic dihydroxy alcohols.
Summary of the invention
The technical problem to be solved is that in prior art washings consumption is big, waste water is intractable after washing asks
Topic, it is provided that a kind of new containing oxirane and the waste gas processing method of expoxy propane.The method have washings consumption little, washing
The tractable advantage of rear waste water.
For solving the problems referred to above, the technical solution used in the present invention is as follows: a kind of useless containing oxirane and expoxy propane
Gas disposal method, the waste gas containing oxirane, expoxy propane enters the first waste gas absorption tower and the contact of the first cleaning mixture is washed
Washing, the waste gas of the first waste gas absorption tower is discharged into the second waste gas absorption tower from tower top, continues to contact with the second cleaning mixture, passes through
After washing, the waste gas being stripped of oxirane or expoxy propane is discharged from the second waste gas absorption top of tower；First waste gas absorption tower
Bottom wash rich solution is sent into the first hydration reactor and is carried out catalysis hydration reaction, the first hydration reactor ethylene oxide, epoxy
Waste water after the conversion reaction of propane enters the first waste gas absorption tower as washings after lithium bromide fridge；Second waste gas is inhaled
Receive tower bottom washing rich solution to send into the second hydration reactor and carry out catalysis hydration reaction, the second hydration reactor ethylene oxide,
Waste water after the conversion reaction of expoxy propane enters second as the second washings after lithium bromide fridge at least partially and gives up
Gas absorption tower.
In technique scheme, it is preferable that the first washings, the second washings fill into fresh water；Second hydration reaction
In device, the waste water after catalytic reaction 0.01～100% enters second as the second washings by weight after lithium bromide fridge
Waste gas absorption tower, remainder enters Waste Water Treatment.
In technique scheme, it is preferable that the first waste gas absorption tower is provided with protection nitrogen feed pipeline, the first waste gas absorption
Top of tower exhaust emission tube line is provided with protection nitrogen feed pipeline；Second waste gas absorption tower is provided with protection nitrogen feed pipeline, the
Two waste gas absorption top of tower exhaust emission tube lines are provided with protection nitrogen and low-pressure steam feeding line.
In technique scheme, it is preferable that containing oxirane, the waste gas ethylene oxide of expoxy propane, expoxy propane
Mass content is 0.001～72%.
In technique scheme, it is preferable that it is anti-that the first hydration reactor and the second hydration reactor are suspension bed catalysis
Answer device, catalyst be selected from Ion exchange resins catalyst, reaction temperature is 10～125 DEG C, reaction pressure be 0.05～
0.15MPa, the washing rich solution time of staying in hydration reactor is 2～15min, enters the oxirane in hydration reactor
It is 0.01～1:1 with the mass ratio of hydration reactor inner catalyst.
In technique scheme, it is preferable that the first waste gas absorption tower operating condition is: the first washings give up with entering first
The mol ratio of the oxirane in gas absorption tower is 2～400:1, and the first temperature of washing water is-15～70 DEG C, normal pressure, theoretical tower
Plate number is 3～30, and the volume ratio entering the protection nitrogen in the first waste gas absorption tower and waste gas is 0.1～1:1；Second waste gas is inhaled
Receiving tower operating condition is: the second washings are 2～400:1 with the mol ratio of the oxirane entered in the second waste gas absorption tower,
Second temperature of washing water is-15～50 DEG C, normal pressure, and theoretical cam curve is 3～30, enters the protection nitrogen in the second waste gas absorption tower
Gas is 0.1～1:1 with the volume ratio of waste gas.
In technique scheme, it is preferable that the compound gold of resinae that catalyst provides selected from Shanghai Petroleum Chemical Engineering Institute
Metal catalyst, reaction temperature is 25～120 DEG C.
In technique scheme, it is preferable that the first waste gas absorption tower operating condition is: the first washings give up with entering first
The mol ratio of the oxirane in gas absorption tower is 4～200:1, and the first temperature of washing water is-15～15 DEG C, and theoretical cam curve is
8～15；Second waste gas absorption tower operating condition is: the matter of the oxirane in the second washings and entrance the second waste gas absorption tower
Amount ratio is 4～200:1, and the second temperature of washing water is-15～15 DEG C, and theoretical cam curve is 8～15.
In technique scheme, it is preferable that described environmental emission standard is that " GB 31571-2015 petro chemical industry is dirty
Dye thing discharge standard "；First hydration reactor or the second hydration reactor ethylene oxide, the conversion ratio of expoxy propane are all higher than
98%.
It is an object of the invention to provide a kind of waste gas processing method Han ethylene oxide/propylene oxide, there are washings and utilize
Rate is high, total energy approach, reduces energy consumption, and after washing, waste liquid is disposable, plant running safety and stability, the recyclable profit of by-product
With, increase the feature of economic benefit.It is a feature of the present invention that being given birth to containing EO/PO waste water after washing by catalysis hydration reaction
Become di-alcohols, owing to glycol solution has good assimilation effect equally to EO/PO, the waste water after hydration reaction can be made
It is circulated absorption for cleaning mixture and reacts again.Solve the washings consumption that the existing waste gas containing EO/PO generally exists big, wash
Wash the problems such as rear waste water is difficult.The dihydroxylic alcohols concentration generated along with catalysis hydration in circulation washes raises, can be to waste gas
The absorption of middle EO/PO has good facilitation effect, for ensureing assimilation effect and reaction mass, and from EO aqueous solution security standpoint
Consider (high concentration EO aqueous solution has inflammability), need to ensure that the water content in washes must be higher than EO content Radix Achyranthis Bidentatae.When washing
When washing dihydroxylic alcohols excessive concentration in recycling waste water, can be in the first waste gas absorption tower overhead reflux line and the second hydration reactor way of escape
High for part containing alcohol waste water is entered sewage disposal system.And supplement equivalent fresh water in tower top cooling line.To meet washings
Amount requirement.Due to dihydroxylic alcohols environmental sound, safety non-toxic, general biochemical treatment can meet environmental requirement.The present invention is with existing
Have technology differs primarily in that the present invention passes through catalysis hydration reaction and reduces the content of EO/PO in washings, and utilizes anti-
Washing should be circulated by washings afterwards.Not only reduce the problems such as potential safety hazard, waste water difficult treatment, improve containing alcohol in waste water
Ratio, it is simple to recycle, greatly reduce washings consumption especially, improves economic benefit, and (puts with catalysis hydration reaction
Thermal response) afterwards lean solution be charging rich solution heat supply as thermal source, reclaimed the energy of system, reached good energy-saving and cost-reducing effect
Really.
Below by embodiment, the invention will be further elaborated, but is not limited only to the present embodiment.
Detailed description of the invention
[embodiment 1]
A kind of containing oxirane with the waste gas processing method of expoxy propane, EGT 120 DEG C, exhaust air mass flow is tail
Gas 817.5kg/h is (containing protection nitrogen N2=55.3wt%, EO=8.1wt%, PO=36.6wt%) by the first waste gas absorption
Tower (theoretical cam curve 12 pieces) washs, and washings are the containing alcohol waste water 15t/h (H of 50 DEG C2O=70wt%, EG=
10wt%, PG=20wt%), after washing, waste gas enters the second waste gas absorption tower (theoretical cam curve 10 pieces) and carries out secondary washing,
Second wash water is the containing alcohol waste water 3t/h (H of 10 DEG C2O=55wt%, EG=15wt%, PG=30wt%).Gas phase after washing
Middle EO, PO content is trace,.First exhaust gas washing tower bottom wash rich solution 15340kg/h (wherein EO content 65.9kg/h,
PO content 299.21kg/h).First exhaust gas washing tower bottom wash rich solution discharging is pumped into the first hydration through the first tower waste water pump
Reactor carries out reacting (exothermic reaction), and (EO/PO hydration generates corresponding binary to the EO/PO in catalysis hydration removes waste water
Alcohol), after reaction, lean solution is back to the first waste gas absorption tower top after entering lithium bromide fridge as fridge power heat source, as
Washings recycle.First hydration reactor temperature 52 DEG C, pressure 0.05MPa.After reaction, ethylene oxide/propylene oxide converts
Rate is 99.99%.First hydration reactor is suspension bed catalytic reactor, internal diameter 1200mm, Catalyst packing effective depth
2700mm, loading catalyst volume 3m3.Catalyst uses Ion exchange resins catalyst.
Second exhaust gas washing tower tower reactor rich solution is pumped to the second water and reactor carries out reacting (heat release through the second tower waste water pump
Reaction), after the EO/PO (EO/PO hydration generates corresponding dihydroxylic alcohols) in catalysis hydration removes waste water, reaction lean solution is through lithium bromide
It is back to the second exhaust gas washing tower tower top after fridge cooling recycle as washings.Second hydration reactor temperature 21
DEG C, pressure 0.05MPa.After reaction, ethylene oxide/propylene oxide conversion ratio is 99.999%.Second hydration reactor is suspension bed
Catalytic reactor, internal diameter 800mm, Catalyst packing effective depth 2500mm, loading catalyst volume 1.26m3.Catalysis hydration is anti-
The by-product that should produce mainly includes ethylene glycol (EG), diethylene glycol (DEG), propylene glycol (PG), dipropylene glycol (DPG) and the most anti-
The nitrogen etc. answered, can carry out subsequent recovery utilization.
[embodiment 2]
A kind of containing oxirane with the waste gas processing method of expoxy propane, EGT 120 DEG C, exhaust air mass flow is tail
Gas 817.5kg/h is (containing protection nitrogen N2=55.3wt%, EO=8.1wt%, PO=36.6wt%) by the first waste gas absorption
Tower (theoretical cam curve 12 pieces) washs, and washings are the containing alcohol waste water 15t/h (H of 60 DEG C2O=70wt%, EG=
10wt%, PG=20wt%), after washing, waste gas enters the second waste gas absorption tower (theoretical cam curve 10 pieces) and carries out secondary washing,
Second wash water is the containing alcohol waste water 3t/h (H of 10 DEG C2O=55wt%, EG=15wt%, PG=30wt%).Gas phase after washing
Middle EO, PO content is trace.First exhaust gas washing tower bottom wash rich solution 15268.27kg/h (wherein EO content
57.935kg/h, PO content 269.496kg/h).First exhaust gas washing tower bottom wash rich solution discharging is through the first tower waste water pump pump
Sending into the first hydration reactor to carry out reacting (exothermic reaction), (EO/PO is hydrated raw the EO/PO in catalysis hydration removes waste water
Become corresponding dihydroxylic alcohols), after reaction, lean solution is back to the first waste gas suction after entering lithium bromide fridge as fridge power heat source
Receive tower top, recycle as washings.First hydration reactor temperature 60.4 DEG C, pressure 0.05MPa.Epoxy second after reaction
Alkane/epoxypropane conversion rate is 99.999%.First hydration reactor is suspension bed catalytic reactor, internal diameter 1200mm, catalysis
Agent filling effective depth 2500mm, loading catalyst volume 2.8m3.Catalyst uses Ion exchange resins catalyst.
Second exhaust gas washing tower tower reactor rich solution is pumped to the second water and reactor carries out reacting (heat release through the second tower waste water pump
Reaction), after the EO/PO (EO/PO hydration generates corresponding dihydroxylic alcohols) in catalysis hydration removes waste water, reaction lean solution is through lithium bromide
It is back to the second exhaust gas washing tower tower top after fridge cooling recycle as washings.Second hydration reactor temperature 31.6
DEG C, pressure 0.05MPa.After reaction, ethylene oxide/propylene oxide conversion ratio is 99.999%.Second hydration reactor is suspension bed
Catalytic reactor, internal diameter 800mm, Catalyst packing effective depth 2200mm, loading catalyst volume 1.1m3.Catalysis hydration is anti-
The by-product that should produce mainly includes ethylene glycol (EG), diethylene glycol (DEG), propylene glycol (PG), dipropylene glycol (DPG) and the most anti-
The nitrogen etc. answered, can carry out subsequent recovery utilization.
[embodiment 3]
A kind of containing oxirane with the waste gas processing method of expoxy propane, EGT 120 DEG C, exhaust air mass flow is tail
Gas 817.5kg/h is (containing protection nitrogen N2=55.3wt%, EO=8.1wt%, PO=36.6wt%) by the first waste gas absorption
Tower (theoretical cam curve 12 pieces) washs, and washings are the containing alcohol waste water 15t/h (H of 75 DEG C2O=70wt%, EG=
10wt%, PG=20wt%), after washing, waste gas enters the second waste gas absorption tower (theoretical cam curve 10 pieces) and carries out secondary washing,
Second wash water is the containing alcohol waste water 3t/h (H of 10 DEG C2O=55wt%, EG=15wt%, PG=30wt%).Gas phase after washing
Middle EO content be 78PPB, PO content be 89PPB.First exhaust gas washing tower bottom wash rich solution 15036.122kg/h (wherein EO
Content 39.681kg/h, PO content 187.511kg/h).First exhaust gas washing tower bottom wash rich solution discharging is through the first tower waste water
Pump is pumped into the first hydration reactor to carry out reacting (exothermic reaction), EO/PO (the EO/PO water in catalysis hydration removes waste water
Symphysis becomes corresponding dihydroxylic alcohols), after reaction, lean solution is useless as being back to first after fridge power heat source entrance lithium bromide fridge
Aspiration receives tower top, recycles as washings.First hydration reactor temperature 69 DEG C, pressure 0.05MPa.Epoxy second after reaction
Alkane/epoxypropane conversion rate is 99.999%.First hydration reactor is suspension bed catalytic reactor, internal diameter 1200mm, catalysis
Agent filling effective depth 2500mm, loading catalyst volume 2.8m3.Catalyst uses Ion exchange resins catalyst.
Second exhaust gas washing tower tower reactor rich solution is pumped to the second water and reactor carries out reacting (heat release through the second tower waste water pump
Reaction), after the EO/PO (EO/PO hydration generates corresponding dihydroxylic alcohols) in catalysis hydration removes waste water, reaction lean solution is through lithium bromide
It is back to the second exhaust gas washing tower tower top after fridge cooling recycle as washings.Second hydration reactor temperature 63.6
DEG C, pressure 0.05MPa.After reaction, ethylene oxide/propylene oxide conversion ratio is 99.999%.Second hydration reactor is suspension bed
Catalytic reactor, internal diameter 800mm, Catalyst packing effective depth 2000mm, loading catalyst volume 1.0m3.Catalysis hydration is anti-
The by-product that should produce mainly includes ethylene glycol (EG), diethylene glycol (DEG), propylene glycol (PG), dipropylene glycol (DPG) and the most anti-
The nitrogen etc. answered, can carry out subsequent recovery utilization.
[embodiment 4]
A kind of containing oxirane with the waste gas processing method of expoxy propane, EGT 120 DEG C, exhaust air mass flow is tail
Gas 817.5kg/h is (containing protection nitrogen N2=55.3wt%, EO=8.1wt%, PO=36.6wt%) by the first waste gas absorption
Tower (theoretical cam curve 12 pieces) washs, and washings are the containing alcohol waste water 15t/h (H of 100 DEG C2O=70wt%, EG=
10wt%, PG=20wt%), after washing, waste gas enters the second waste gas absorption tower (theoretical cam curve 10 pieces) and carries out secondary washing,
Second wash water is the containing alcohol waste water 3t/h (H of 10 DEG C2O=55wt%, EG=15wt%, PG=30wt%).Gas phase after washing
Middle EO content be 0.037%wt, PO content be 0.141%wt.First exhaust gas washing tower bottom wash rich solution 14885.545kg/h
(wherein EO content 42.765kg/h, PO content 205.735kg/h).First exhaust gas washing tower bottom wash rich solution discharging is through first
Tower waste water pump is pumped into the first hydration reactor to carry out reacting (exothermic reaction), the EO/PO in catalysis hydration removes waste water
(EO/PO hydration generates corresponding dihydroxylic alcohols), after reaction, lean solution refluxes after entering lithium bromide fridge as fridge power heat source
To the first waste gas absorption tower top, recycle as washings.First hydration reactor temperature 87 DEG C, pressure 0.18MPa.Reaction
Rear ethylene oxide/propylene oxide conversion ratio is 99.999%.First hydration reactor is suspension bed catalytic reactor, internal diameter
1200mm, Catalyst packing effective depth 2300mm, loading catalyst volume 2.6m3.Catalyst uses Ion exchange resins
Catalyst.
Second exhaust gas washing tower tower reactor rich solution is pumped to the second water and reactor carries out reacting (heat release through the second tower waste water pump
Reaction), after the EO/PO (EO/PO hydration generates corresponding dihydroxylic alcohols) in catalysis hydration removes waste water, reaction lean solution is through lithium bromide
It is back to the second exhaust gas washing tower tower top after fridge cooling recycle as washings.Second hydration reactor temperature 99.4
DEG C, pressure 0.05MPa.After reaction, ethylene oxide/propylene oxide conversion ratio is 99.999%.Second hydration reactor is suspension bed
Catalytic reactor, internal diameter 800mm, Catalyst packing effective depth 1600mm, loading catalyst volume 0.8m3.Catalysis hydration is anti-
The by-product that should produce mainly includes ethylene glycol (EG), diethylene glycol (DEG), propylene glycol (PG), dipropylene glycol (DPG) and the most anti-
The nitrogen etc. answered, can carry out subsequent recovery utilization.
[embodiment 5]
A kind of containing oxirane with the waste gas processing method of expoxy propane, EGT 120 DEG C, exhaust air mass flow is tail
Gas 924.954kg/h is (containing protection nitrogen N2=88.18wt%, EO=0wt%, PO=11.82wt%) inhaled by the first waste gas
Receiving tower (theoretical cam curve 19 pieces) to wash, washings are the containing alcohol waste water 28t/h (H of 70 DEG C2O=70wt%, EG=
30wt%, PG=0wt%), after washing, waste gas enters the second waste gas absorption tower (theoretical cam curve 19 pieces) and carries out secondary washing, and two
Secondary washings are the containing alcohol waste water 4.63t/h (H of 10 DEG C2O=70wt%, EG=30wt%, PO=wt%).After washing in gas phase
It is 1PPM that EO content is respectively 0PPB, PO content.First exhaust gas washing tower bottom wash rich solution temperature 62.5 DEG C, flow
27981kg/h (wherein EO content 0kg/h, PO content 108.814kg/h).First exhaust gas washing tower bottom wash rich solution discharging warp
First tower waste water pump is pumped into the first hydration reactor to carry out reacting (exothermic reaction), the EO/ in catalysis hydration removes waste water
PO (EO/PO hydration generates corresponding dihydroxylic alcohols), after reaction, lean solution is returned after entering lithium bromide fridge as fridge power heat source
It flow to the first waste gas absorption tower top, recycle as washings.First hydration reactor temperature 62.5 DEG C, pressure 1MPa.Instead
Should ethylene oxide/propylene oxide conversion ratio be 99.999% afterwards.First hydration reactor is suspension bed catalytic reactor, internal diameter
1200mm, Catalyst packing effective depth 5000mm, loading catalyst volume 5.6m3.Catalyst uses Ion exchange resins
Catalyst.
Second exhaust gas washing tower tower reactor rich solution is pumped to the second water and reactor carries out reacting (heat release through the second tower waste water pump
Reaction), after the EO/PO (EO/PO hydration generates corresponding dihydroxylic alcohols) in catalysis hydration removes waste water, reaction lean solution is through lithium bromide
Fridge cooling after 100% be back to the second exhaust gas washing tower tower top as washings recycle, remaining enter waste water process
System.Second hydration reactor temperature 35.4 DEG C, pressure 1MPa.After reaction, ethylene oxide/propylene oxide conversion ratio is
99.999%.Second hydration reactor is suspension bed catalytic reactor, internal diameter 800mm, Catalyst packing effective depth 2500mm,
Loading catalyst volume 1.26m3.The by-product that catalysis hydration reaction produces mainly includes propylene glycol (PG), dipropylene glycol (DPG)
And unreacted nitrogen etc., subsequent recovery utilization can be carried out.
[embodiment 6]
A kind of containing oxirane with the waste gas processing method of expoxy propane, EGT 120 DEG C, exhaust air mass flow is tail
Gas 924.954kg/h is (containing protection nitrogen N2=88.18wt%, EO=0wt%, PO=11.82wt%) inhaled by the first waste gas
Receiving tower (theoretical cam curve 19 pieces) to wash, washings are the containing alcohol waste water 28t/h (H of 40 DEG C2O=70wt%, EG=
30wt%, PO=0wt%), after washing, waste gas enters the second waste gas absorption tower (theoretical cam curve 19 pieces) and carries out secondary washing, and two
Secondary washings are the containing alcohol waste water 4.6t/h (H of 10 DEG C2O=70wt%, EG=30wt%, PG=0wt%).After washing in gas phase
It is trace that EO content is respectively 0PPB, PO content.First exhaust gas washing tower bottom wash rich solution temperature 40.4 DEG C, flow
28101.71kg/h (wherein EO content 0kg/h, PO content 109.33kg/h).First exhaust gas washing tower bottom wash rich solution discharging
It is pumped into the first hydration reactor through the first tower waste water pump to carry out reacting (exothermic reaction), in catalysis hydration removes waste water
EO/PO (EO/PO hydration generates corresponding dihydroxylic alcohols), after after reaction, lean solution enters lithium bromide fridge as fridge power heat source
It is back to the first waste gas absorption tower top, recycles as washings.First hydration reactor temperature 40.4 DEG C, pressure 1MPa.
After reaction, ethylene oxide/propylene oxide conversion ratio is 99.999%.First hydration reactor is suspension bed catalytic reactor, internal diameter
1200mm, Catalyst packing effective depth 5500mm, loading catalyst volume 6.2m3.Catalyst uses Ion exchange resins
Catalyst.
Second exhaust gas washing tower tower reactor rich solution is pumped to the second water and reactor carries out reacting (heat release through the second tower waste water pump
Reaction), after the EO/PO (EO/PO hydration generates corresponding dihydroxylic alcohols) in catalysis hydration removes waste water, reaction lean solution is through lithium bromide
Fridge cooling after 100% be back to the second exhaust gas washing tower tower top as washings recycle, remaining enter waste water process
System.Second hydration reactor temperature 16.5 DEG C, pressure 1MPa.After reaction, ethylene oxide/propylene oxide conversion ratio is
99.999%.Second hydration reactor is suspension bed catalytic reactor, internal diameter 800mm, Catalyst packing effective depth 2800mm,
Loading catalyst volume 1.4m3.The by-product that catalysis hydration reaction produces mainly includes propylene glycol (PG), dipropylene glycol (DPG)
And unreacted nitrogen etc., subsequent recovery utilization can be carried out.
[embodiment 7]
A kind of containing oxirane with the waste gas processing method of expoxy propane, EGT 250 DEG C, exhaust air mass flow is tail
Gas 924.954kg/h is (containing protection nitrogen N2=88.18wt%, EO=0wt%, PO=11.82wt%) inhaled by the first waste gas
Receiving tower (theoretical cam curve 19 pieces) to wash, washings are the containing alcohol waste water 28t/h (H of 80 DEG C2O=70wt%, EG=
30wt%, PG=0wt%), after washing, waste gas enters the second waste gas absorption tower (theoretical cam curve 19 pieces) and carries out secondary washing, and two
Secondary washings are the containing alcohol waste water 4.6t/h (H of 10 DEG C2O=70wt%, EG=30wt%, PG=0wt%).After washing in gas phase
It is 162PPM that EO content is respectively 0PPB, PO content.First exhaust gas washing tower bottom wash rich solution temperature 78.5 DEG C, flow
27993.446kg/h (wherein EO content 0kg/h, PO content 162.148kg/h).First exhaust gas washing tower bottom wash rich solution goes out
Material is pumped into the first hydration reactor through the first tower waste water pump to carry out reacting (exothermic reaction), in catalysis hydration removes waste water
EO/PO (EO/PO hydration generates corresponding dihydroxylic alcohols), after after reaction, lean solution enters lithium bromide fridge as fridge power heat source
It is back to the first waste gas absorption tower top, recycles as washings.First hydration reactor temperature 78.5 DEG C, pressure 1MPa.
After reaction, ethylene oxide/propylene oxide conversion ratio is 99.999%.First hydration reactor is suspension bed catalytic reactor, internal diameter
1200mm, Catalyst packing effective depth 4000mm, loading catalyst volume 4.5m3.Catalyst uses Ion exchange resins
Catalyst.
Second exhaust gas washing tower tower reactor rich solution is pumped to the second water and reactor carries out reacting (heat release through the second tower waste water pump
Reaction), after the EO/PO (EO/PO hydration generates corresponding dihydroxylic alcohols) in catalysis hydration removes waste water, reaction lean solution is through lithium bromide
Fridge cooling after 100% be back to the second exhaust gas washing tower tower top as washings recycle, remaining enter waste water process
System.Second hydration reactor temperature 46.3 DEG C, pressure 1MPa.After reaction, ethylene oxide/propylene oxide conversion ratio is
99.999%.Second hydration reactor is suspension bed catalytic reactor, internal diameter 800mm, Catalyst packing effective depth 2300mm,
Loading catalyst volume 1.15m3.The by-product that catalysis hydration reaction produces mainly includes propylene glycol (PG), dipropylene glycol (DPG)
And unreacted nitrogen etc., subsequent recovery utilization can be carried out.
Claims (9)
1., containing oxirane and a waste gas processing method for expoxy propane, the waste gas containing oxirane, expoxy propane enters the
One waste gas absorption tower and the contact of the first cleaning mixture are washed, and the waste gas of the first waste gas absorption tower is discharged into second from tower top and gives up
Gas absorption tower, continues to contact with the second cleaning mixture, after washing, is stripped of the waste gas of oxirane or expoxy propane from second
Waste gas absorption top of tower is discharged；The first hydration reactor sent into by first waste gas absorption tower bottom wash rich solution, and to carry out catalysis hydration anti-
Should, the first hydration reactor ethylene oxide, expoxy propane conversion reaction after waste water after lithium bromide fridge as washing
Wash water and enter the first waste gas absorption tower；Second waste gas absorption tower bottom wash rich solution is sent into the second hydration reactor and is carried out catalytic water
Close reaction, the second hydration reactor ethylene oxide, expoxy propane conversion reaction after waste water at least partially through lithium bromide
The second waste gas absorption tower is entered as the second washings after fridge.
The most according to claim 1 containing oxirane and the waste gas processing method of expoxy propane, it is characterised in that the first washing
Water, the second washings fill into fresh water；Waste water after catalytic reaction by weight 0.01～100% in second hydration reactor
Entering the second waste gas absorption tower as the second washings after lithium bromide fridge, remainder enters Waste Water Treatment.
The most according to claim 1 containing oxirane and the waste gas processing method of expoxy propane, it is characterised in that the first waste gas
Absorption tower is provided with protection nitrogen feed pipeline, and the first waste gas absorption top of tower exhaust emission tube line is provided with protection nitrogen feed pipe
Line；Second waste gas absorption tower is provided with protection nitrogen feed pipeline, and the second waste gas absorption top of tower exhaust emission tube line is provided with protection
Nitrogen and low-pressure steam feeding line.
The most according to claim 1 containing oxirane and the waste gas processing method of expoxy propane, it is characterised in that containing epoxy second
Alkane, the waste gas ethylene oxide of expoxy propane, the mass content of expoxy propane are 0.001～72%.
The most according to claim 1 containing oxirane and the waste gas processing method of expoxy propane, it is characterised in that the first hydration
Reactor and the second hydration reactor are suspension bed catalytic reactor, and catalyst is selected from Ion exchange resins catalyst, instead
Answering temperature is 10～125 DEG C, and reaction pressure is 0.05～0.15MPa, and the washing rich solution time of staying in hydration reactor is 2
～15min, the mass ratio entering the oxirane in hydration reactor and hydration reactor inner catalyst is 0.01～1:1.
6. according to containing oxirane and the waste gas processing method of expoxy propane described in claim 1 or 3, it is characterised in that first gives up
Gas absorption tower operating condition is: the mol ratio of the first washings and the oxirane entered in the first waste gas absorption tower be 2～
400:1, the first temperature of washing water is-15～70 DEG C, normal pressure, and theoretical cam curve is 3～30, enters in the first waste gas absorption tower
Protection nitrogen is 0.1～1:1 with the volume ratio of waste gas；Second waste gas absorption tower operating condition is: the second washings with enter the
The mol ratio of the oxirane in two waste gas absorption towers is 2～400:1, and the second temperature of washing water is-15～50 DEG C, normal pressure, reason
The opinion number of plates is 3～30, and the volume ratio entering the protection nitrogen in the second waste gas absorption tower and waste gas is 0.1～1:1.
The most according to claim 5 containing oxirane and the waste gas processing method of expoxy propane, it is characterised in that catalyst selects
The resinae composite metal catalyst provided from Shanghai Petroleum Chemical Engineering Institute, reaction temperature is 25～120 DEG C.
The most according to claim 6 containing oxirane and the waste gas processing method of expoxy propane, it is characterised in that the first waste gas
Absorption tower operating condition is: the first washings are 4～200 with the mol ratio of the oxirane entered in the first waste gas absorption tower:
1, the first temperature of washing water is-15～15 DEG C, and theoretical cam curve is 8～15；Second waste gas absorption tower operating condition is: second washes
The mass ratio washing water and the oxirane entered in the second waste gas absorption tower is 4～200:1, the second temperature of washing water be-15～
15 DEG C, theoretical cam curve is 8～15.
The most according to claim 1 containing oxirane and the waste gas processing method of expoxy propane, it is characterised in that described environmental protection
Discharge standard is " GB 31571-2015 petro chemical industry pollutant emission standard "；First hydration reactor or the second hydration
Reactor ethylene oxide, the conversion ratio of expoxy propane are all higher than 98%.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106861372A (en) * | 2017-03-23 | 2017-06-20 | 中石化上海工程有限公司 | Waste gas processing method containing EO, PO |
| CN106955563A (en) * | 2017-03-23 | 2017-07-18 | 中石化上海工程有限公司 | Waste gas processing method containing EO and PO |
| CN106984138A (en) * | 2017-03-27 | 2017-07-28 | 中石化上海工程有限公司 | waste gas processing method |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000010692A1 (en) * | 1998-08-24 | 2000-03-02 | Environ Ingenieurgesellschaft Für Innovative Umwelttechnische Verfahren Mbh | Method and device for disposing of ethylene oxide gas |
| JP2007245106A (en) * | 2006-03-20 | 2007-09-27 | Miura Co Ltd | Gas treatment system |
| CN101121641A (en) * | 2006-08-10 | 2008-02-13 | 中国石化扬子石油化工有限公司 | Method for preparing ethylene glycol by catalytic hydration method |
| CN104014227A (en) * | 2014-06-05 | 2014-09-03 | 万华化学集团股份有限公司 | Method for purifying organic waste gas containing epoxypropane or ethylene oxide |
-
2016
- 2016-09-30 CN CN201610877129.XA patent/CN106310879A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000010692A1 (en) * | 1998-08-24 | 2000-03-02 | Environ Ingenieurgesellschaft Für Innovative Umwelttechnische Verfahren Mbh | Method and device for disposing of ethylene oxide gas |
| JP2007245106A (en) * | 2006-03-20 | 2007-09-27 | Miura Co Ltd | Gas treatment system |
| CN101121641A (en) * | 2006-08-10 | 2008-02-13 | 中国石化扬子石油化工有限公司 | Method for preparing ethylene glycol by catalytic hydration method |
| CN104014227A (en) * | 2014-06-05 | 2014-09-03 | 万华化学集团股份有限公司 | Method for purifying organic waste gas containing epoxypropane or ethylene oxide |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106861372A (en) * | 2017-03-23 | 2017-06-20 | 中石化上海工程有限公司 | Waste gas processing method containing EO, PO |
| CN106955563A (en) * | 2017-03-23 | 2017-07-18 | 中石化上海工程有限公司 | Waste gas processing method containing EO and PO |
| CN106984138A (en) * | 2017-03-27 | 2017-07-28 | 中石化上海工程有限公司 | waste gas processing method |
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