CN109248564A - A kind of recycle device and technique of the ammonia liquor that petrochemical industry refinery acidity water treatment facilities generates - Google Patents
A kind of recycle device and technique of the ammonia liquor that petrochemical industry refinery acidity water treatment facilities generates Download PDFInfo
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- CN109248564A CN109248564A CN201811359123.9A CN201811359123A CN109248564A CN 109248564 A CN109248564 A CN 109248564A CN 201811359123 A CN201811359123 A CN 201811359123A CN 109248564 A CN109248564 A CN 109248564A
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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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/02—Preparation, purification or separation of ammonia
- C01C1/024—Purification
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/20—Reductants
- B01D2251/206—Ammonium compounds
- B01D2251/2062—Ammonia
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
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Abstract
The present invention provides a kind of recycle devices of ammonia liquor, comprising: acidic water stripping device；The ammonia liquor sedimentation device being connected is exported with the ammonia liquor of the acidic water stripping device；The primary filter being connected is exported with the ammonia liquor sedimentation device；The ammonia liquor treatment tank being connected is exported with the primary filter；The fine filter being connected is exported with the ammonia liquor treatment tank；The SNCR flue gas denitrification system being connected is exported with the fine filter.The ammonia liquor that the present invention steams acidic water stripping device is used in boiler system SNCR flue-gas denitration process, both the processing problem of above-mentioned ammonia liquor had been solved, reduce the cost of environmental pollution and outer committee's processing, the cost of material of boiler SNCR technique denitrfying agent ammonium hydroxide is also reduced simultaneously, to a large amount of ammonium hydroxide required for providing in original SNCR flue-gas denitration process, the sustainable development idea of environmental protection with benefit win-win is reached.
Description
Technical field
The invention belongs to the ammonia liquor reutilization technology fields that acid water treatment facilities generates, and are related to a kind of returning for ammonia liquor
Receive a kind of recycle device of the ammonia liquor generated using device and technique more particularly to petrochemical industry refinery acidity water treatment facilities
And technique.
Background technique
Petrochemical industry refinery acid water is one of petrochemical industry refining most common waste water of enterprise, is due to existing in petroleum and products thereof
Sulfur-containing compound and nitrogenous compound, Atmospheric vacuum, catalytic cracking, thermal cracking, delayed coking, reformed pre-hydrogenated, hydrofinishing,
It is hydrocracked etc. in process, these compounds can pass through the reactions such as Pintsch process, catalytic cracking, catalytic hydrogenation and generate sulfur-bearing
Compound and nitrogenous compound, and enter in product stream, these product streams pass through condensation dehydration or washing process, that is, generate
Sulfur-bearing ammonia-containing water is commonly called as sulfur-containing waste water or acid water.This acid water is in atmospheric and vacuum distillation tower top separator, catalytic cracking point
Evaporate overhead separator, catalytic cracking compression rich gas drain sump, coking fractional distillation column top separator and oil hydrogenation cracking plus hydrogen
It can be generated in the equipment such as the high and low pressure separator of purification, and outside the vulcanisation hydrogen of the pollutant in acid water and ammonia, also
Oil, phenol, cyanogen etc., while acid Sulfide in water is different with processing unit (plant) with crude oil type with ammonia density and change.Usually by stone
Change the acid water that refinery generates to be divided into: non-phenol acid water, acid water containing phenol and desalter acid water.
Based on environmentally protective idea of development, these acid waters contain a large amount of ammonia and hydrogen sulfide and other impurities and
Organic matter.It is absolutely not to allow outlet, so subsequent processing must be carried out to it.In addition to desalter acid water, other are acid
Water is at present in existing conventional treatment process, using it is more be exactly sewage stripping process flow, mainly have single column low pressure
Stripping process, double tower pressurization stripping process and single column pressurization extraction stripping process.Among these, the stripper plant of most number can steam
Ammonia and hydrogen sulfide in acid water out, wherein one material is the thick gas ammonia (ammonia liquor) of the hydrogen sulfide with lower content.For
Secondary pollution is avoided, part factory handles the thick gas in this part by the way of burning the technique ammonia liquor that ammonia process or water absorb
Ammonia, part factory use technology for refining ammonia.Burning ammonia process is to burn up a large amount of ammonia, has both caused the waste of resource, could also
Generate a large amount of NOXExhaust gas pollutes environment.And water absorption technique is to absorb thick ammonia with water, 20% or so thick ammonia of generation
Water, due to containing hydrogen sulfide in ammonia liquor, utility value is little, and outer committee is needed to be handled.
Therefore, a kind of suitable method how is found, the ammonia liquor after these sewage strippings is handled, is made
It can preferably be recycled, it has also become one of many relevant enterprise urgent problems to be solved in the industry.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is that providing the recycle device and work of a kind of ammonia liquor
Skill, the recycle device and technique of the ammonia liquor that especially a kind of petrochemical industry refinery acidity water treatment facilities generates.The present invention mentions
The recycle device and technique of confession, after treatment by the ammonia liquor after sewage stripping, the SNCR cigarette for boiler system
Gas denitrating technique, not only solves the processing problem of ammonia liquor, and greatly reduce the raw material of denitration of boiler smoke technique at
This, while process route is simple, is suitble to industrialized production.
The present invention provides a kind of recycle devices of ammonia liquor, comprising: acidic water stripping device；
The ammonia liquor sedimentation device being connected is exported with the ammonia liquor of the acidic water stripping device；
The primary filter being connected is exported with the ammonia liquor sedimentation device；
The ammonia liquor treatment tank being connected is exported with the primary filter；
The fine filter being connected is exported with the ammonia liquor treatment tank；
The SNCR flue gas denitrification system being connected is exported with the fine filter.
Preferably, the acidic water stripping device includes soul water stripper；
The ammonia liquor sedimentation device includes ammonia liquor settling tank；
Overflow plate is provided in the ammonia liquor sedimentation device；
The ammonia liquor sedimentation device is provided with water inlet；
The ammonia liquor sedimentation device includes the first ammonia liquor sedimentation device being arranged in parallel and the second ammonia liquor sedimentation dress
It sets.
Preferably, the overflow plate is arranged in the short transverse of the ammonia liquor sedimentation device；
The ammonia liquor sedimentation device is arranged under having into lower inlet and outlet out；
The primary filter includes one of basket filter, cartridge filter and self-cleaning filter or a variety of；
The precision of the primary filter is 150~300 μm.
Preferably, the recycle device further includes reflux mixing arrangement；
The ammonia liquor outlet of the acidic water stripping device is connected with the first import of the reflux mixing arrangement；
The outlet of the ammonia liquor sedimentation device is connected with the second import of the reflux mixing arrangement；
It is connected with the outlet of the reflux mixing arrangement with the import of the ammonia liquor sedimentation device；
Overflow plate is provided in the ammonia liquor treatment tank.
Preferably, the reflux mixing arrangement includes pipe-line mixer, eddy mixer, air and liquid mixer and static mixing
One of device is a variety of；
The overflow plate is arranged in the short transverse of the ammonia liquor treatment tank；
The ammonia liquor treatment tank is arranged under having into lower inlet and outlet out；
The fine filter exports the SNCR flue gas denitrification system being connected specifically: the SNCR flue gas denitrification system
Ammonium hydroxide import be connected with the outlet of the fine filter.
Preferably, the fine filter includes that accurate filter, sintering web filter and metal twine in wind filter
It is one or more；
The precision of the fine filter is 50~100 μm；
The SNCR flue gas denitrification system includes the SNCR flue gas denitrification system of coal water slurry boiler；
The ammonium hydroxide import of the SNCR flue gas denitrification system is connected with the ammonium hydroxide aerosol spray head of SNCR flue gas denitrification system.
The present invention also provides a kind of recycling techniques of ammonia liquor, comprising the following steps:
1) ammonia liquor after being settled the ammonia liquor that sewage stripping technique steams, after being settled；
2) ammonia liquor after the sedimentation for obtaining above-mentioned steps obtains secondary product after primary filter；
3) secondary product for obtaining above-mentioned steps obtains three step products after purification sedimentation；
4) the three step products for obtaining above-mentioned steps obtain purification ammonium hydroxide, it is de- to be sent into SNCR flue gas after refining filtering
It is recycled in nitre technique.
Preferably, the acid water includes the acid water of petrochemical industry refinery production；
The ammonia liquor, by mass percentage, including 15%~25% ammonia, 0.5%~2% hydrogen sulfide, 1%~
10% suspended matter, 0.01%~0.1% volatile phenol and 65%~85% water；
COD content is 18000~35000mg/L in the ammonia liquor；
The sedimentation further includes the steps that being diluted with water；
The time of the sedimentation is 20~60h；
The temperature of the sedimentation is 30~40 DEG C.
Preferably, the step 1) specifically:
11) it after the ammonia liquor after settling ammonia liquor and a part that sewage stripping technique steams is mixed, obtains
Mixture；
12) ammonia liquor after the mixture for obtaining above-mentioned steps is settled, after being settled；
13) ammonia liquor after a part sedimentation is back to mixing step, after the ammonia liquor after another part sedimentation enters
Continuous step.
Preferably, the reflux ratio of the reflux is (2~4): 1；
The time of the purification sedimentation is 20~60h；
The temperature of the purification sedimentation is 22~30 DEG C；
The SNCR flue-gas denitration process is specially SNCR denitrating flue gas aerosol spray ammonia process.
The present invention provides a kind of recycle devices of ammonia liquor, comprising: acidic water stripping device；With the acid water
The ammonia liquor of stripper plant exports the ammonia liquor sedimentation device being connected；It is connected with ammonia liquor sedimentation device outlet first
Grade filter；The ammonia liquor treatment tank being connected is exported with the primary filter；It is connected with ammonia liquor treatment tank outlet
The fine filter connect；The SNCR flue gas denitrification system being connected is exported with the fine filter.Compared with prior art, originally
The acid water containing a large amount of ammonia and hydrogen sulfide that invention is steamed for the normal stripper plant of existing oil refining, can be using burning ammonia
The mode for the technique ammonia liquor that technique or water absorb handles the thick gas ammonia in this part.And it burns ammonia process and had both caused the wave of resource
Take, can also generate a large amount of NOXExhaust gas pollutes environment；And 20% or so the ammonia liquor that water absorption technique generates, due to ammonia liquor
In contain hydrogen sulfide, utility value is little, and outer committee is needed to carry out many defects such as handling.
The ammonia liquor that acidic water stripping device is steamed of the invention is used for boiler system SNCR denitrating flue gas work
It in skill, had both solved the processing problem of above-mentioned ammonia liquor, and had reduced the cost of environmental pollution and outer committee's processing, also reduce simultaneously
The cost of material of boiler SNCR technique denitrfying agent ammonium hydroxide, to a large amount of ammonia required for being provided in original SNCR flue-gas denitration process
Water has reached the sustainable development idea of environmental protection with benefit win-win.
The ammonia liquor of further inventive of the present invention steamed to acidic water stripping device has carried out a series of particular procedures, makes it
It can be used in coal water slurry boiler system SNCR flue-gas denitration process, by injecting a large amount of treated ammonia liquor in furnace,
With itself and NOXReaction generates nitrogen, to reduce boiler smoke NOXDischarge, saved in original SNCR flue-gas denitration process,
The expense of ammonium hydroxide more than 20% concentration of outsourcing.After the present invention is diluted by the purified water generated using sewage stripping, obtain
The ammonia liquor of 20% concentration, while double tanks are carried out to ammonia liquor and are replaced, after settlement treatment, reselection filter carried out impurity
Filter after further increasing ammonia liquor quality, is recycled into ammonia liquor treatment tank, after carrying out refining filtering again, obtains boiler
Denitration ammonium hydroxide.
The experimental results showed that the recycle device and technique of ammonia liquor provided by the invention are reached instead of outsourcing ammonium hydroxide
The processing for solving the problems, such as sewage stripping ammonia liquor has been arrived, while having decreased the buying expenses of denitration ammonium hydroxide, had both been reached
Environment protection emission, and being capable of energy saving expense.
Detailed description of the invention
Fig. 1 is the master of the recycle device for the ammonia liquor that petrochemical industry refinery acidity water treatment facilities provided by the invention generates
Want process flow diagram.
Specific embodiment
In order to further appreciate that the present invention, the preferred embodiments of the invention are described below with reference to embodiment, but
It is it should be appreciated that these descriptions only require the invention patent to further illustrate the features and advantages of the present invention
Limitation.
All raw materials of the present invention, are not particularly limited its source, buying on the market or according to those skilled in the art
The preparation of conventional method known to member.
All raw materials of the present invention, are not particularly limited its purity, and present invention preferably employs technical pure or coal water slurry boilers
The conventional purity of system SNCR flue-gas denitration process ingredient requirement.
The expression of all nouns of the present invention and referred to as belong to this field routine noun expression and referred to as, each noun expression and
Referred to as in its related application field be it is explicit, those skilled in the art express and referred to as according to noun, Neng Gouqing
Chu is accurately uniquely understood.
The present invention provides a kind of recycle devices of ammonia liquor, comprising: acidic water stripping device；
The ammonia liquor sedimentation device being connected is exported with the ammonia liquor of the acidic water stripping device；
The primary filter being connected is exported with the ammonia liquor sedimentation device；
The ammonia liquor treatment tank being connected is exported with the primary filter；
The fine filter being connected is exported with the ammonia liquor treatment tank；
The SNCR flue gas denitrification system being connected is exported with the fine filter.
The mode being connected is not particularly limited in the present invention, with well known to those skilled in the art technologic normal
Connection type is advised, those skilled in the art can select according to practical condition, raw material condition and product requirement
Select and adjust, it is of the present invention be connected be connected preferably by pipeline, or be connected by pipeline with pump.The present invention couple
Relevant control and monitoring device on the pipeline are not particularly limited, and those skilled in the art can be according to actual production feelings
Condition, raw material condition and product requirement are selected and are adjusted.
The acidic water stripping device and its specific structure is not particularly limited in the present invention, ripe with those skilled in the art
The technologic conventional acid water stripper plant and structure known, those skilled in the art can according to practical condition,
Raw material condition and product requirement are selected and are adjusted, and acidic water stripping device of the present invention preferably refers to petrochemical industry refinery
Acidic water stripping device is specifically as follows soul water stripper.
The present invention is in principle not particularly limited the ammonia liquor sedimentation device, and those skilled in the art can be according to reality
The border condition of production, raw material condition and product requirement are selected and are adjusted, and the present invention is preferably to realize the thick of complicated component
The removal of impurities of ammonium hydroxide, the ammonia liquor sedimentation device preferably include ammonia liquor settling tank.
The present invention is in principle not particularly limited the internal structure of the ammonia liquor sedimentation device, those skilled in the art
It can be selected and be adjusted according to practical condition, raw material condition and product requirement, the present invention is preferably to be implemented as
Divide the removal of impurities of complicated ammonia liquor, while realizing the removal to upper layer suspended matter and lower sediment, while also helping industry even
It connects, overflow plate is provided in the ammonia liquor sedimentation device, the overflow plate is more preferably along the height of the ammonia liquor sedimentation device
Degree side is set up.Ammonia liquor sedimentation device of the present invention is arranged under preferably having into lower inlet and outlet out.
The present invention is preferably to realize the removal of impurities of the ammonia liquor of complicated component, while realizing and sinking to upper layer suspended matter and lower layer
The removal in shallow lake, while subsequent applications are also helped, the ammonia liquor sedimentation device is preferably additionally provided with water inlet, more specific preferred
Top for ammonia liquor sedimentation device is provided with water inlet.Its role is to realize diluting effect, simultaneously during sedimentation
Water inlet is arranged in top, is more advantageous to efficiently separating for various weight impurity in ammonia liquor infall process.
The present invention is more preferable complete and refinement integral device process, is more advantageous to continuous mass production in actual industrial, institute
It states ammonia liquor sedimentation device and preferably includes the first ammonia liquor sedimentation device being arranged in parallel and the second ammonia liquor sedimentation device, i.e., it is excellent
Be selected as the first ammonia liquor settling tank being arranged in parallel and the second ammonia liquor settling tank, thus realize double tanks displacements, deposition it is continuous
Change production model.
The invention also includes export the primary filter being connected with the ammonia liquor sedimentation device.The present invention is in principle
The type selecting and precision of the primary filter are not particularly limited, those skilled in the art can according to practical condition,
Raw material condition and product requirement are selected and are adjusted, and the present invention is preferably to realize the removal of impurities of the ammonia liquor of complicated component,
Realize the removal to Multiple components, the primary filter preferably includes basket filter, cartridge filter and self-cleaning filtering
One of device is a variety of, more preferably basket filter, cartridge filter or self-cleaning filter.The primary filter
Precision is preferably 150~300 μm, more preferably 180~280 μm, more preferably 200~250 μm.
The present invention is preferably to realize the removal of impurities of the ammonia liquor of complicated component, improves treatment effect, more preferable complete and refinement
Integral device process, is more advantageous to continuous mass production in actual industrial, recycle device of the present invention it is also preferable to include
Flow back mixing arrangement.Wherein, the first import of the ammonia liquor outlet of the acidic water stripping device and the reflux mixing arrangement
It is connected；The outlet of the ammonia liquor sedimentation device is connected with the second import of the reflux mixing arrangement；With the reflux
The outlet of mixing arrangement is connected with the import of the ammonia liquor sedimentation device.
The present invention is in principle not particularly limited the type selecting of the reflux mixing arrangement, and those skilled in the art can root
It is selected and is adjusted according to practical condition, raw material condition and product requirement, the present invention is preferably to realize complicated component
Ammonia liquor removal of impurities, realize the effect of reflow treatment, the reflux mixing arrangement preferably includes pipe-line mixer, whirlpool mixing
One of device, air and liquid mixer and static mixer are a variety of, and more preferably pipe-line mixer, eddy mixer, gas-liquid are mixed
Clutch or static mixer.
The present invention is in principle not particularly limited the internal structure of the ammonia liquor treatment tank, and those skilled in the art can
To be selected and be adjusted according to practical condition, raw material condition and product requirement, the present invention is preferably to realize ingredient
The removal of impurities of complicated ammonia liquor, while realizing that the purification to upper layer suspended matter and lower sediment removes, while also helping industry
It connects, is provided with overflow plate in the ammonia liquor treatment tank, the overflow plate is more preferably along the height of the ammonia liquor treatment tank
Side is set up.Ammonia liquor treatment tank of the present invention is arranged under preferably having into lower inlet and outlet out.
The invention also includes export the fine filter being connected with the ammonia liquor treatment tank.The present invention is right in principle
The type selecting and precision of the fine filter are not particularly limited, and those skilled in the art can be according to practical condition, original
Material situation and product requirement are selected and are adjusted, and the present invention is preferably to realize that the accurate of ammonia liquor of complicated component removes
It is miscellaneous, realize accurate removal to remaining ingredient, the fine filter preferably include accurate filter, sintering web filter and
Metal twines one of wind filter or a variety of, and more preferably accurate filter, sintering web filter or metal winds silk mistake
Filter.The precision of the fine filter is preferably 50~100 μm, more preferably 60~90 μm, more preferably 70~80 μm.
The invention also includes export the SNCR flue gas denitrification system being connected with the fine filter.The present invention is to institute
The specific process for stating SNCR flue gas denitrification system is not particularly limited, with SNCR denitrating flue gas well known to those skilled in the art system
The normal process steps of system, those skilled in the art can carry out according to practical condition, raw material condition and product requirement
Selection and adjustment, the present invention are preferably to realize the application of ammonia liquor, and the SNCR flue gas denitrification system preferably refers to water-coal-slurry
The SNCR flue gas denitrification system of boiler.Wherein the ammonium hydroxide import of the SNCR flue gas denitrification system preferably with SNCR denitrating flue gas system
The ammonium hydroxide aerosol spray head of system is connected, i.e., is connected with the ammonium hydroxide aerosol spray head in the boiler.In the present invention, the ammonium hydroxide
Aerosol spray head is also connected with the pipeline for being filled with air.
The present invention also provides a kind of recycling techniques of ammonia liquor, comprising the following steps:
1) ammonia liquor after being settled the ammonia liquor that sewage stripping technique steams, after being settled；
2) ammonia liquor after the sedimentation for obtaining above-mentioned steps obtains secondary product after primary filter；
3) secondary product for obtaining above-mentioned steps obtains three step products after purification sedimentation；
4) the three step products for obtaining above-mentioned steps obtain purification ammonium hydroxide, it is de- to be sent into SNCR flue gas after refining filtering
It is recycled in nitre technique.
Selection and composition of the present invention to required equipment in the recycling technique of above-mentioned ammonia liquor, and it is corresponding preferred
The selection of corresponding equipment and composition and corresponding optimum principle in principle, with the recycle device of aforementioned ammonia liquor
It can be corresponded to, this is no longer going to repeat them.
Ammonia liquor after the present invention first settles the ammonia liquor that sewage stripping technique steams, after being settled.
The present invention is in principle not particularly limited the design parameter of the ammonia liquor, with well known to those skilled in the art
The conventional ratio for the ammonia liquor that sewage stripping technique steams, those skilled in the art can according to practical condition,
Raw material condition and product requirement are selected and are adjusted, the integrated artistic process and device of recycling and reusing of the present invention,
It is all based on the content for the ammonia liquor that sewage stripping technique steams and especially sets, in the present invention, the acid water is excellent
Choosing includes the acid water of petrochemical industry refinery production.
The ammonia liquor, by mass percentage, specifically include 15%~25% ammonia, 0.5%~2% hydrogen sulfide,
1%~10% suspended matter, 0.01%~0.1% volatile phenol and 65%~85% water.Wherein, the content of ammonia is more specific
It is 17%~23%, more specifically 19%~21%.The content of hydrogen sulfide is more specifically 0.8%~1.8%, more specifically
1.0%~1.5%.The content of suspended matter is more specifically 3%~8%, more specifically 5%~6%.The content of volatile phenol is more specific
It is 0.03%~0.08%, more specifically 0.05%~0.06%.The content of water is more specifically 67%~83%, more specifically
70%~80%, more specifically 72%~78%.COD content is specially 18000~35000mg/L in the ammonia liquor, more
Body is 20000~33000mg/L, more specifically 23000~30000mg/L, more specifically 25000~28000mg/L.
The present invention is in principle not particularly limited the condition of the sedimentation, and those skilled in the art can be according to practical life
It produces situation, raw material condition and product requirement to be selected and adjusted, the present invention is preferably to improve effect of settling, reduces thick ammonia
The content of various impurity in water, preferably in subsequent boiler SNCR flue-gas denitration process, the time of the sedimentation is preferably
20~60h, more preferably 25~55h, more preferably 30~50h, more preferably 35~45h.The temperature of the sedimentation is preferably
30~40 DEG C, more preferably 32~38 DEG C, more preferably 34~36 DEG C.
The present invention is preferably to realize the removal of impurities of the ammonia liquor of complicated component, while realizing and sinking to upper layer suspended matter and lower layer
The removal in shallow lake, while also helping subsequent applications, the sedimentation further includes the steps that being diluted with water, more specifically preferably acid water
The purified water that stripping generates is diluted.This method can not only realize diluting effect during sedimentation, and more advantageous
Various weight impurity efficiently separates in ammonia liquor infall process.
The present invention is preferably to realize the removal of impurities of the ammonia liquor of complicated component, improves treatment effect, more preferable complete and refinement
Integral device process is more advantageous to continuous mass production in actual industrial, the step 1) of the present invention specifically:
11) it after the ammonia liquor after settling ammonia liquor and a part that sewage stripping technique steams is mixed, obtains
Mixture；
12) ammonia liquor after the mixture for obtaining above-mentioned steps is settled, after being settled；
13) ammonia liquor after a part sedimentation is back to mixing step, after the ammonia liquor after another part sedimentation enters
Continuous step.
Present invention preferably provides reflux hybrid techniques, and by the ammonia liquor after sedimentation, a part is back to mixing step, i.e.,
11), the ammonia liquor after another part sedimentation enters subsequent step, i.e., 2), to preferably improve effect of settling, is more advantageous to
Industrialize continuous production.It is mixed that mixed mode of the present invention preferably includes pipeline mixing, whirlpool mixing, gas-liquid mixed and static state
One of conjunction is a variety of, more preferably pipeline mixing, whirlpool mixing, gas-liquid mixed or static mixing.
The present invention is in principle not particularly limited the reflux ratio of the reflux, and those skilled in the art can be according to reality
The condition of production, raw material condition and product requirement are selected and are adjusted, and the present invention is preferably to improve the mixed effect that flows back,
And then effect of settling is improved, and it is more advantageous to industrialization continuous production, the reflux ratio of the reflux is preferably (2~4): 1, more preferably
For (2.2~3.8): 1, more preferably (2.5~3.5): 1, more preferably (2.7~3.3): 1.
Ammonia liquor after the sedimentation that the present invention then obtains above-mentioned steps obtains secondary product after primary filter.
The present invention is in principle not particularly limited the mode and precision of the primary filter, and those skilled in the art can be with
It is selected and is adjusted according to practical condition, raw material condition and product requirement, the present invention is preferably to realize that ingredient is multiple
The removal of impurities of miscellaneous ammonia liquor, realizes the removal to Multiple components, and the mode of the primary filter preferably includes basket filtering, cartridge type
One of filtering and self-cleaning filtering are a variety of, more preferably basket filtering, barrel type filtering or self-cleaning filtering.The primary
The precision of filtering is preferably 150~300 μm, more preferably 180~280 μm, more preferably 200~250 μm.
The secondary product that the present invention again obtains above-mentioned steps obtains three step products after purification sedimentation.
The present invention is in principle not particularly limited the condition of the purification sedimentation, and those skilled in the art can be according to reality
The border condition of production, raw material condition and product requirement are selected and are adjusted, and the present invention is preferably to improve secondary refining sedimentation
Effect, reduce the content of various trace impurities in ammonia liquor, preferably in subsequent boiler SNCR flue-gas denitration process, institute
The time for stating purification sedimentation is preferably 20~60h, more preferably 25~55h, more preferably 30~50h, more preferably 35~
45h.The temperature of the purification sedimentation is preferably 22~30 DEG C, more preferably 24~28 DEG C, more preferably 25~27 DEG C.
The three step products that the present invention finally obtains above-mentioned steps obtain purification ammonium hydroxide, are sent into after refining filtering
It is recycled in SNCR flue-gas denitration process.
The present invention is in principle not particularly limited the mode and precision of the refining filtering, and those skilled in the art can be with
It is selected and is adjusted according to practical condition, raw material condition and product requirement, the present invention is preferably to realize that ingredient is multiple
The accurate removal of impurities of miscellaneous ammonia liquor, realizes the accurate removal to remaining ingredient, and the mode of the refining filtering preferably includes essence
It is close filtering, sintering net filtration and metal winding silk filtering one of or it is a variety of, more preferably secondary filter, sintering net filtration or
Metal winds silk filtering.The precision of the fine filter is preferably 50~100 μm, and more preferably 60~90 μm, more preferably
70~80 μm.
The present invention is preferably to realize the application of ammonia liquor, and the SNCR flue-gas denitration process preferably refers to coal water slurry boiler
SNCR flue-gas denitration process.The SNCR flue-gas denitration process is particularly preferred as SNCR denitrating flue gas aerosol spray ammonia process.
Referring to Fig. 1, Fig. 1 is the recycling for the ammonia liquor that petrochemical industry refinery acidity water treatment facilities provided by the invention generates
The technical process schematic diagram of device.Wherein, A is acid water, and B is ammonia, and C is purified water, and D is purification wind；1, acid steam
Stripper, 2, mixer, 3, ammonia liquor tank (1), 4, ammonia liquor tank (2), 5, ammonia liquor pump (1), 6, ammonia liquor pump (2), 7, filtering
Device (1), 8, smart ammonia water tank (1), 9, smart aqua ammonia pump, 10, filter (2), 11, spray gun, 12, boiler.
The present invention provides the recycle devices and work of the ammonia liquor that a kind of petrochemical industry refinery acidity water treatment facilities generates
Skill, the ammonia liquor that acidic water stripping device is steamed are used in boiler system SNCR flue-gas denitration process, have both been solved above-mentioned thick
The processing problem of ammonium hydroxide, reduces the cost of environmental pollution and outer committee's processing, while also reducing boiler SNCR technique denitrfying agent
The cost of material of ammonium hydroxide has reached environmental protection and effect to a large amount of ammonium hydroxide required for providing in original SNCR flue-gas denitration process
The sustainable development idea of beneficial win-win.
The ammonia liquor of further inventive of the present invention steamed to acidic water stripping device has carried out a series of particular procedures, makes it
It can be used in coal water slurry boiler system SNCR flue-gas denitration process, by injecting a large amount of treated ammonia liquor in furnace,
With itself and NOXReaction generates nitrogen, to reduce boiler smoke NOXDischarge, saved in original SNCR flue-gas denitration process,
The expense of ammonium hydroxide more than 20% concentration of outsourcing.After the present invention is diluted by the purified water generated using sewage stripping, obtain
The ammonia liquor of 20% concentration, while the double tanks for carrying out specific structure to ammonia liquor and importing and exporting position are replaced, at sedimentation and dilution
After reason, deposition effect is further more preferably promoted to it using reflux mixing arrangement, reselection filter is filtered impurity,
After further increasing ammonia liquor quality, the ammonia liquor treatment tank into specific structure and inlet and outlet position is recycled, is carried out again
After refining filtering, Denitration in Boiler ammonium hydroxide is obtained.The experimental results showed that the recycle device of ammonia liquor provided by the invention and
Technique has reached the processing for solving the problems, such as sewage stripping ammonia liquor instead of outsourcing ammonium hydroxide, while decreasing denitration ammonia
The buying expenses of water have not only reached environment protection emission, but also being capable of energy saving expense.
In order to further illustrate the present invention, with reference to embodiments to a kind of recycling of ammonia liquor provided by the invention
Device and technique are described in detail, but it is to be understood that these embodiments be under the premise of the technical scheme of the present invention into
Row is implemented, and the detailed implementation method and specific operation process are given, only to further illustrate feature of the invention and excellent
Point, rather than limiting to the claimed invention, protection scope of the present invention are also not necessarily limited to following embodiments.
Embodiment 1
Referring to Fig. 1, Fig. 1 is the recycling for the ammonia liquor that petrochemical industry refinery acidity water treatment facilities provided by the invention generates
The technical process schematic diagram of device.
The recycle device of ammonia liquor of the invention, including soul water stripper, reflux mixing arrangement, the first ammonia liquor
Settling tank, the second ammonia liquor settling tank, primary filter, ammonia liquor treatment tank, fine filter and coal water slurry boiler.
Wherein, the ammonia liquor outlet of soul water stripper is connected with the import of reflux mixing arrangement, and flow back mixing arrangement
Thick ammonia outlet be connected respectively with the first ammonia liquor settling tank and the second ammonia liquor settling tank, and the first ammonia liquor settling tank and
It is arranged in parallel between second ammonia liquor settling tank.
Water inlet, and the civilian post among tank body are respectively arranged in first ammonia liquor settling tank and the second ammonia liquor settling tank
It is provided with overflow plate in the height direction, meanwhile, the first ammonia liquor settling tank and the second ammonia liquor sedimentation pot bottom are provided with slightly
The inlet and outlet of ammonium hydroxide, the two are arranged oppositely, realize under ammonia liquor into it is lower go out.
The outlet of the ammonia liquor of first ammonia liquor settling tank and the second ammonia liquor settling tank respectively with reflux mixing arrangement the
One feed inlet is connected with second charging aperture, is also connected with the feed inlet of primary filter (300 μm of precision).Primary filter
Discharge port be connected with the feed inlet of ammonia liquor treatment tank, (precision is for the discharge port of ammonia liquor treatment tank and fine filter
100 μm) feed inlet be connected, ammonia of the discharge port of fine filter directly with SNCR flue gas denitrification system in coal water slurry boiler
The spray head of water sprinkler system is connected.
The acid water that petrochemical industry refinery is produced steams ammonia liquor (flow: 14000m after sewage stripping technique3/ h,
Temperature: 100 DEG C, pressure 0.2Mpa) be sent into reflux mixing arrangement after, then remove the first ammonia liquor settling tank and/or the second ammonia liquor
Settling tank is settled, while purified water (the purification water flow 30m generated using sewage stripping3/ h, temperature: 35 DEG C, pressure
Steam-water mixing and dilution 0.45Mpa) are carried out to it, temperature controls the ammonia liquor at 40 DEG C, after being settled after 30h.
Wherein, ammonia liquor by mass percentage, including 25% ammonia, 2% hydrogen sulfide, 7.9% suspended matter,
0.1% volatile phenol and 65% water；COD content is 35000mg/L.
After sedimentation, suspended matter is reduced to 3% or so in ammonia liquor.
The ammonia liquor that reflux mixing arrangement comes out can be settled through the first ammonia liquor settling tank, can also be through the second thick ammonia
Water settling tank, can also be simultaneously through the first ammonia liquor settling tank and the second ammonia liquor settling tank.The two is arranged in parallel, and can be cut
It changes, treating capacity can be improved, realize continuous sedimentation process, while being also convenient for technology controlling and process and maintenance.
Ammonia liquor after the first ammonia liquor settling tank and the sedimentation of the second ammonia liquor settling tank, a part are into precision
300 μm of primary filter, another part are back to reflux mixing arrangement, and reflux ratio is (2~4): 1, enhance treatment effect.Through
Secondary product (suspended matter is reduced to 1% or so) after crossing primary filter, then at 35 DEG C, after purification sedimentation for 24 hours, obtain
Three step products.Then after precision is 100 μm of refining filtering, ammonia liquor suspended matter is reduced to 0.05% or so, COD content
8000~10000mg/L, temperature: 30 DEG C, pressure 0.4Mpa is injected into boiler spray gun directly as denitrfying agent, reaches removing
The purpose of boiler smoke nitrogen oxides.
Technical solution provided by the invention is counted, 15%~20% ammonia vol 200kg/h can be saved, and
The coal water slurry boiler exhaust gas volumn of 35t/h is according to 100000m3/ h, boiler smoke nitrogen oxides is by concentration 600mg/m3It is down to 100mg/
m3It calculates, saves 3,500,000 yuan/year of ammonium hydroxide acquisition expenses.Corresponding ammonia liquor processing cost is also reduced simultaneously.
Embodiment 2
Referring to Fig. 1, Fig. 1 is the recycling for the ammonia liquor that petrochemical industry refinery acidity water treatment facilities provided by the invention generates
The technical process schematic diagram of device.
The recycle device of ammonia liquor of the invention, including soul water stripper, reflux mixing arrangement, the first ammonia liquor
Settling tank, the second ammonia liquor settling tank, primary filter, ammonia liquor treatment tank, fine filter and coal water slurry boiler.
Wherein, the ammonia liquor outlet of soul water stripper is connected with the import of reflux mixing arrangement, and flow back mixing arrangement
Thick ammonia outlet be connected respectively with the first ammonia liquor settling tank and the second ammonia liquor settling tank, and the first ammonia liquor settling tank and
It is arranged in parallel between second ammonia liquor settling tank.
Water inlet, and the civilian post among tank body are respectively arranged in first ammonia liquor settling tank and the second ammonia liquor settling tank
It is provided with overflow plate in the height direction, meanwhile, the first ammonia liquor settling tank and the second ammonia liquor sedimentation pot bottom are provided with slightly
The inlet and outlet of ammonium hydroxide, the two are arranged oppositely, realize under ammonia liquor into it is lower go out.
The outlet of the ammonia liquor of first ammonia liquor settling tank and the second ammonia liquor settling tank respectively with reflux mixing arrangement the
One feed inlet is connected with second charging aperture, is also connected with the feed inlet of primary filter (precision is 200 μm).Primary filter
The discharge port of device is connected with the feed inlet of ammonia liquor treatment tank, the discharge port and fine filter (precision of ammonia liquor treatment tank
Be 80 μm) feed inlet be connected, the discharge port of fine filter directly with SNCR flue gas denitrification system in coal water slurry boiler
The spray head of ammonia spray system is connected.
The acid water that petrochemical industry refinery is produced steams ammonia liquor (flow: 14000m after sewage stripping technique3/ h,
Temperature: 100 DEG C, pressure 0.2Mpa) be sent into reflux mixing arrangement after, then remove the first ammonia liquor settling tank and/or the second ammonia liquor
Settling tank is settled, while purified water (the purification water flow 35m generated using sewage stripping3/ h, temperature: 33 DEG C, pressure
Steam-water mixing and dilution 0.45Mpa) are carried out to it, temperature controls the ammonia liquor at 35 DEG C, after being settled after 36h.
Wherein, ammonia liquor by mass percentage, including 25% ammonia, 2% hydrogen sulfide, 7.9% suspended matter,
0.1% volatile phenol and 65% water；COD content is 35000mg/L.
After sedimentation, suspended matter is reduced to 2.8% or so in ammonia liquor.
The ammonia liquor that reflux mixing arrangement comes out can be settled through the first ammonia liquor settling tank, can also be through the second thick ammonia
Water settling tank, can also be simultaneously through the first ammonia liquor settling tank and the second ammonia liquor settling tank.The two is arranged in parallel, and can be cut
It changes, treating capacity can be improved, realize continuous sedimentation process, while being also convenient for technology controlling and process and maintenance.
Ammonia liquor after the first ammonia liquor settling tank and the sedimentation of the second ammonia liquor settling tank, a part are into precision
150~300 μm of primary filter, another part are back to reflux mixing arrangement, and reflux ratio is (2~4): 1, enhancing processing effect
Fruit.Secondary product (suspended matter is reduced to 1% or so) after primary filter, then at 33 DEG C, for 24 hours by purification sedimentation
Afterwards, three step products are obtained.Then after precision is 80 μm of refining filtering, ammonia liquor suspended matter is reduced to 0.04% or so,
COD 6000~8000mg/L of content, temperature: 28 DEG C, pressure 0.4Mpa is injected into boiler spray gun directly as denitrfying agent, reaches
To the purpose of removing boiler smoke nitrogen oxides.
Technical solution provided by the invention is counted, 15%~20% ammonia vol 200kg/h can be saved, and
The coal water slurry boiler exhaust gas volumn of 35t/h is according to 100000m3/ h, boiler smoke nitrogen oxides is by concentration 600mg/m3It is down to 100mg/
m3It calculates, saves 3,500,000 yuan/year of ammonium hydroxide acquisition expenses.Corresponding ammonia liquor processing cost is also reduced simultaneously.
Embodiment 3
Referring to Fig. 1, Fig. 1 is the recycling for the ammonia liquor that petrochemical industry refinery acidity water treatment facilities provided by the invention generates
The technical process schematic diagram of device.
The recycle device of ammonia liquor of the invention, including soul water stripper, reflux mixing arrangement, the first ammonia liquor
Settling tank, the second ammonia liquor settling tank, primary filter, ammonia liquor treatment tank, fine filter and coal water slurry boiler.
Wherein, the ammonia liquor outlet of soul water stripper is connected with the import of reflux mixing arrangement, and flow back mixing arrangement
Thick ammonia outlet be connected respectively with the first ammonia liquor settling tank and the second ammonia liquor settling tank, and the first ammonia liquor settling tank and
It is arranged in parallel between second ammonia liquor settling tank.
Water inlet, and the civilian post among tank body are respectively arranged in first ammonia liquor settling tank and the second ammonia liquor settling tank
It is provided with overflow plate in the height direction, meanwhile, the first ammonia liquor settling tank and the second ammonia liquor sedimentation pot bottom are provided with slightly
The inlet and outlet of ammonium hydroxide, the two are arranged oppositely, realize under ammonia liquor into it is lower go out.
The outlet of the ammonia liquor of first ammonia liquor settling tank and the second ammonia liquor settling tank respectively with reflux mixing arrangement the
One feed inlet is connected with second charging aperture, is also connected with the feed inlet of primary filter (precision is 150 μm).Primary filter
The discharge port of device is connected with the feed inlet of ammonia liquor treatment tank, the discharge port and fine filter (precision of ammonia liquor treatment tank
Be 50 μm) feed inlet be connected, the discharge port of fine filter directly with SNCR flue gas denitrification system in coal water slurry boiler
The spray head of ammonia spray system is connected.
The acid water that petrochemical industry refinery is produced steams ammonia liquor (flow: 14000m after sewage stripping technique3/ h,
Temperature: 100 DEG C, pressure 0.2Mpa) be sent into reflux mixing arrangement after, then remove the first ammonia liquor settling tank and/or the second ammonia liquor
Settling tank is settled, while purified water (the purification water flow 35m generated using sewage stripping3/ h, temperature: 33 DEG C, pressure
Steam-water mixing and dilution 0.45Mpa) are carried out to it, temperature controls the ammonia liquor at 35 DEG C, after being settled after 36h.
Wherein, ammonia liquor by mass percentage, including 25% ammonia, 2% hydrogen sulfide, 7.9% suspended matter,
0.1% volatile phenol and 65% water；COD content is 35000mg/L.
After sedimentation, suspended matter is reduced to 2.5% or so in ammonia liquor.
The ammonia liquor that reflux mixing arrangement comes out can be settled through the first ammonia liquor settling tank, can also be through the second thick ammonia
Water settling tank, can also be simultaneously through the first ammonia liquor settling tank and the second ammonia liquor settling tank.The two is arranged in parallel, and can be cut
It changes, treating capacity can be improved, realize continuous sedimentation process, while being also convenient for technology controlling and process and maintenance.
Ammonia liquor after the first ammonia liquor settling tank and the sedimentation of the second ammonia liquor settling tank, a part are into precision
150~300 μm of primary filter, another part are back to reflux mixing arrangement, and reflux ratio is (2~4): 1, enhancing processing effect
Fruit.Secondary product (suspended matter is reduced to 1% or so) after primary filter, then at 33 DEG C, for 24 hours by purification sedimentation
Afterwards, three step products are obtained.Then after precision is 50 μm of refining filtering, ammonia liquor suspended matter is reduced to 0.035% or so,
COD 5000~7000mg/L of content, temperature: 28 DEG C, pressure 0.4Mpa is injected into boiler spray gun directly as denitrfying agent, reaches
To the purpose of removing boiler smoke nitrogen oxides.
Technical solution provided by the invention is counted, 15%~20% ammonia vol 200kg/h can be saved, and
The coal water slurry boiler exhaust gas volumn of 35t/h is according to 100000m3/ h, boiler smoke nitrogen oxides is by concentration 600mg/m3It is down to 100mg/
m3It calculates, saves 3,500,000 yuan/year of ammonium hydroxide acquisition expenses.Corresponding ammonia liquor processing cost is also reduced simultaneously.
Above to a kind of recycling dress for the ammonia liquor that petrochemical industry refinery acidity water treatment facilities generates provided by the invention
It sets and is described in detail with technique, specific case used herein explains the principle of the present invention and embodiment
It states, the above description of the embodiment is only used to help understand the method for the present invention and its core ideas, including best mode, and
But also any person skilled in the art can practice the present invention, including any device or system of manufacture and use, and real
The method for applying any combination.It should be pointed out that for those skilled in the art, not departing from the principle of the invention
Under the premise of, it can be with several improvements and modifications are made to the present invention, these improvement and modification also fall into the claims in the present invention
Protection scope in.The range of the invention patent protection is defined by the claims, and may include those skilled in the art's energy
The other embodiments enough expected.If there is these other embodiments the structure for being not different from claim character express to want
Element, or if they include the equivalent structural elements with the character express of claim without essence difference, these other
Embodiment should also be included in the scope of the claims.
Claims (10)
1. a kind of recycle device of ammonia liquor characterized by comprising acidic water stripping device；
The ammonia liquor sedimentation device being connected is exported with the ammonia liquor of the acidic water stripping device；
The primary filter being connected is exported with the ammonia liquor sedimentation device；
The ammonia liquor treatment tank being connected is exported with the primary filter；
The fine filter being connected is exported with the ammonia liquor treatment tank；
The SNCR flue gas denitrification system being connected is exported with the fine filter.
2. recycle device according to claim 1, which is characterized in that the acidic water stripping device includes acid water
Stripper；
The ammonia liquor sedimentation device includes ammonia liquor settling tank；
Overflow plate is provided in the ammonia liquor sedimentation device；
The ammonia liquor sedimentation device is provided with water inlet；
The ammonia liquor sedimentation device includes the first ammonia liquor sedimentation device and the second ammonia liquor sedimentation device being arranged in parallel.
3. recycle device according to claim 2, which is characterized in that the overflow plate is settled along the ammonia liquor and filled
It is arranged in the short transverse set；
The ammonia liquor sedimentation device is arranged under having into lower inlet and outlet out；
The primary filter includes one of basket filter, cartridge filter and self-cleaning filter or a variety of；
The precision of the primary filter is 150~300 μm.
4. recycle device according to any one of claims 1 to 3, which is characterized in that the recycle device
It further include reflux mixing arrangement；
The ammonia liquor outlet of the acidic water stripping device is connected with the first import of the reflux mixing arrangement；
The outlet of the ammonia liquor sedimentation device is connected with the second import of the reflux mixing arrangement；
It is connected with the outlet of the reflux mixing arrangement with the import of the ammonia liquor sedimentation device；
Overflow plate is provided in the ammonia liquor treatment tank.
5. recycle device according to claim 4, which is characterized in that the reflux mixing arrangement includes pipeline mixing
One of device, eddy mixer, air and liquid mixer and static mixer are a variety of；
The overflow plate is arranged in the short transverse of the ammonia liquor treatment tank；
The ammonia liquor treatment tank is arranged under having into lower inlet and outlet out；
The fine filter exports the SNCR flue gas denitrification system being connected specifically: the ammonia of the SNCR flue gas denitrification system
Water inlet is connected with the outlet of the fine filter.
6. recycle device according to claim 5, which is characterized in that the fine filter includes secondary filter
Device, sintering web filter and metal twine one of wind filter or a variety of；
The precision of the fine filter is 50~100 μm；
The SNCR flue gas denitrification system includes the SNCR flue gas denitrification system of coal water slurry boiler；
The ammonium hydroxide import of the SNCR flue gas denitrification system is connected with the ammonium hydroxide aerosol spray head of SNCR flue gas denitrification system.
7. a kind of recycling technique of ammonia liquor, which comprises the following steps:
1) ammonia liquor after being settled the ammonia liquor that sewage stripping technique steams, after being settled；
2) ammonia liquor after the sedimentation for obtaining above-mentioned steps obtains secondary product after primary filter；
3) secondary product for obtaining above-mentioned steps obtains three step products after purification sedimentation；
4) the three step products for obtaining above-mentioned steps obtain purification ammonium hydroxide, are sent into SNCR denitrating flue gas work after refining filtering
It is recycled in skill.
8. recycling technique according to claim 7, which is characterized in that the acid water includes what petrochemical industry refinery produced
Acid water；
The ammonia liquor, by mass percentage, including 15%~25% ammonia, 0.5%~2% hydrogen sulfide, 1%~10%
Suspended matter, 0.01%~0.1% volatile phenol and 65%~85% water；
COD content is 18000~35000mg/L in the ammonia liquor；
The sedimentation further includes the steps that being diluted with water；
The time of the sedimentation is 20~60h；
The temperature of the sedimentation is 30~40 DEG C.
9. recycling technique according to claim 7, which is characterized in that the step 1) specifically:
11) it after the ammonia liquor after settling ammonia liquor and a part that sewage stripping technique steams is mixed, is mixed
Object；
12) ammonia liquor after the mixture for obtaining above-mentioned steps is settled, after being settled；
13) ammonia liquor after a part sedimentation is back to mixing step, the ammonia liquor after another part sedimentation enters subsequent step
Suddenly.
10. recycling technique according to claim 9, which is characterized in that the reflux ratio of the reflux is (2~4): 1；
The time of the purification sedimentation is 20~60h；
The temperature of the purification sedimentation is 22~30 DEG C；
The SNCR flue-gas denitration process is specially SNCR denitrating flue gas aerosol spray ammonia process.
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