CN106830428A - A kind of method processed as the devil liquor recovery that absorbent combined desulfurization and denitrification process is produced slag - Google Patents
A kind of method processed as the devil liquor recovery that absorbent combined desulfurization and denitrification process is produced slag Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
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- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
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- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/36—Nitrates
- C01F11/44—Concentrating; Crystallisating; Dehydrating; Preventing the absorption of moisture or caking
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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- C02F1/72—Treatment of water, waste water, or sewage by oxidation
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- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/74—Treatment of water, waste water, or sewage by oxidation with air
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- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/18—Nature of the water, waste water, sewage or sludge to be treated from the purification of gaseous effluents
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2301/00—General aspects of water treatment
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Abstract
The invention provides a kind of method processed as the devil liquor recovery that absorbent combined desulfurization and denitrification process is produced slag, SO will be absorbed first2And NOxThe waste liquid separation of solid and liquid of certain total salt concentration is reached afterwards, then to addition quick lime in the liquid phase obtained after separation and/or white lime adjustment pH, the pH of filtrate is adjusted to 57 after filtering, filtrate is passed through in micro-nano bubble generator, be nitrate by the nitrite complete oxidation in filtrate, pass through subsequent evaporation again, concentration, crystallization, filtering, the operation such as dry, obtains nitric acid calcium product.Subsequent technique as metallurgical slag combined desulfurization and denitration method of the invention, solve the problems, such as that the waste liquid produced in the art production process causes secondary pollution, nitrite is fully converted to nitrate, realize in waste liquid N element all of, obtain pure nitric acid calcium product, the product reaches industrial calcium nitrate and agricultural calcium nitrate national standard simultaneously, has a good application prospect.
Description
Technical field
The present invention relates to environmental protection and Sewage treatment field, and in particular to a kind of de- as absorbent combined desulfurization to slag
The method of the devil liquor recovery treatment that nitre technique is produced.
Background technology
In recent years, with the raising of China's industrialized level, economic rapid growth, State of Air pollution is increasingly serious,
SO2And NOxDischarge capacity it is increasing.The country is for containing SO2And NOxGas, it is necessary to qualified discharge after treatment.
In desulfurization denitration method disclosed in prior art, it is related to the technique of ammonia process to there are long flow path, NH_3 leakage, needs and urges
The problems such as agent；And it is high using dry desulfurization out-of-stock cost, removal efficiency is low；Using nano level material desulphurization denitration, there is system
The problems such as standby high cost, industrialization amplification difficulty.At the same time, China's metallurgical slag discharge capacity is very big, and utilization rate is very low, long
The accumulation of phase is stored up and do not only take up a large amount of soils, and pollution of ecological environment, also causes significant wastage to resource.Metallurgical slag
In containing a large amount of f-CaO in alkalescence, if can be applied in desulphurization denitration, it will produce huge economic benefit.
A kind of method of utilization metallurgical slag combined desulfurization and denitration is disclosed in CN10482648A, is replaced using metallurgical slag
SO in the absorbent slurry absorption flue gas being made for raw material for quick lime or ammonia2And NOx.The invention with metallurgical slag as raw material,
Can effectively alleviate the pollution to environment, and resource waste；It is simultaneously that desulphurization denitration is integrated, absorb SO2And NOx
Absorbent slurry afterwards can be recycled, cost-effective, realize inexpensive flue gas combined desulfurization and denitration, with good economy
Benefit and wide industrial applications prospect.
However, the handling process can produce substantial amounts of desulphurization denitration waste liquid, due to metallurgical slag complicated component, cause joint de-
Zwitterion species is various in sulphur denitration waste liquid, and NO is contained simultaneously3 -、NO2 -、SO4 2-、SO3 2-、HSO4 -、HSO3 -Deng anion and
Mg2+、Ca2+、Mn2+Or Fe3+Deng cation, it is difficult to processed.And NO therein3 -And NO2 -Mix, and NO2 -It is difficult
To be fully oxidized, therefore when subsequent recovery treatment is carried out to waste liquid, hardly result in pure nitrate products.
The content of the invention
In view of problems of the prior art, it is an object of the invention to slag as absorbent combined desulfurization and denitration
The waste liquid produced in technical process is recycled, and prepares pure nitric acid calcium product.
It is that, up to this purpose, the present invention uses following technical scheme：
In a first aspect, the present invention provides a kind of devil liquor recovery produced as absorbent combined desulfurization and denitrification process to slag
The method for the treatment of, the described method comprises the following steps：
(1) waste liquid that slag is produced as absorbent combined desulfurization and denitrification process is carried out into separation of solid and liquid；
(2) removed to addition quick lime in the liquid obtained after step (1) separation of solid and liquid and/or white lime regulation pH
It is miscellaneous, the completely rear filtering of precipitation；
(3) pH of the filtrate for obtaining step (2) is adjusted to 5-7, then carries out oxygen by micro-nano bubble generator
Change；
(4) crystallized after the liquid evaporation concentration obtained after step (3) is aoxidized, filtering is dried, and obtains nitric acid calcium product.
The present invention is used as " a kind of method of utilization metallurgical slag combined desulfurization and denitration " disclosed in patent CN10482648A
Subsequent technique, mainly recycles to slag as the waste liquid produced during absorbent combined desulfurization and denitrification process, makes
Standby pure nitric acid calcium product, realizes recycling the resource of waste liquid.Zwitterion kind in slag combined desulfurization and denitration waste liquid
Class is various, mainly including NO3 -、NO2 -、SO4 2-、SO3 2-、HSO4 -、HSO3 -Deng anion and Mg2+、Ca2+、Mn2+、Fe3+Deng sun from
Son, pH is in faintly acid.The present invention will absorb SO first2And NOxSlag slurries (i.e. waste liquid) solid-liquid of certain total salt concentration is reached afterwards
Separate to remove solid impurity therein, then to addition quick lime in the liquid phase obtained after separation and/or white lime adjustment pH,
Purpose is precipitation except NO3 -、NO2 -、Ca2+Outside other foreign ions, while bring into abundance Ca2+, by the pH of filtrate after filtering
Filtrate, for nitrite ion oxidation provides weak acid environment, is then passed through micro-nano bubble generator by regulation to 5-7
In, the nitrite complete oxidation in filtrate is nitrate by control condition, then by subsequent evaporation, concentration, crystallization is filtered,
The operation such as dry, obtains pure nitric acid calcium product.Realize the recovery whole to N element in waste liquid.
Waste liquid of the present invention refers to absorption SO2And NOxIts total salt concentration is the slag slurries of 10-60wt% afterwards.
According to the present invention, in step (1) described waste liquid the content of slag be 1-30wt%, for example can be 1wt%,
Specific point value between 5wt%, 10wt%, 15wt%, 20wt%, 25wt% or 30wt%, and above-mentioned numerical value, as space is limited
And for concise consideration, the present invention specific point value that no longer scope described in exclusive list includes.
According to the present invention, NO is contained in step (1) described waste liquid3 -And NO2 -。
According to the present invention, SO is contained in step (1) described waste liquid4 2-、SO3 2-、HSO4 -Or HSO3 -In at least one, example
SO can such as be contained4 2-、SO3 2-、HSO4 -Or HSO3 -In any one, typical but non-limiting is combined as：SO4 2-With
SO3 2-；HSO4 -And HSO3 -；SO4 2-、SO3 2-And HSO4 -；SO4 2-And HSO4 -；SO3 2-、HSO4 -And HSO3 -；SO4 2-、SO3 2-、HSO4 -
And HSO3 -Deng as space is limited and for concise consideration, the present invention no longer exclusive list.
According to the present invention, Mg is contained in step (1) described waste liquid2+、Ca2+、Mn2+Or Fe3+In at least two, for example may be used
To contain Mg simultaneously2+And Ca2+；Mn2+And Fe3+；Mg2+And Mn2+；Mg2+And Fe3+；Ca2+And Mn2+；Ca2+And Fe3+；Mg2+、Ca2+
And Mn2+；Mg2+、Ca2+And Fe3+；Ca2+、Mn2+And Fe3+；Mg2+、Ca2+、Mn2+And Fe3+。
According to the present invention, the pH of step (1) described waste liquid is 4-7, for example, can be 4,4.5,5,5.5,6,6.5 or 7, with
And the specific point value between above-mentioned numerical value, as space is limited and for concise consideration, scope no longer described in exclusive list of the invention
Including specific point value.
According to the present invention, the total concentration of the salt that step (1) described waste liquid contains is 10-60wt%, for example, can be
10wt%, 15wt%, 20wt%, 25wt%, 30wt%, 35wt%, 40wt%, 45wt%, 50wt%, 55wt% or
Specific point value between 60wt%, and above-mentioned numerical value, as space is limited and for concise consideration, the present invention no longer exclusive list
The specific point value that the scope includes.
Present invention selection method well known in the art carries out separation of solid and liquid to waste liquid, and particular determination is not done to this, exemplary
, the mode of the separation of solid and liquid can be filtered, settle or suspension etc., but non-be only limitted to this.
According to the present invention, the feed postition of step (2) quick lime and/or white lime is thrown and/or wet throwing for dry.
PH to 9-13 is adjusted after quick lime and/or white lime are added according to the present invention, in step (2), for example can be 9,
9.5th, the specific point value between 10,10.5,11,12,12.5 or 13, and above-mentioned numerical value, examines as space is limited and for concise
Consider, the present invention specific point value that no longer scope described in exclusive list includes.
Precipitation completely after in the filtrate that is filtrated to get containing calcium nitrate and calcium nitrite, calcium nitrate and calcium nitrite are difficult point
From, and calcium nitrite is difficult to be fully oxidized, 1:Its mixed crystallization can be used as concrete additive in the range of 1, but be used
Amount is not high, and pure calcium nitrate is wider in industry and agriculturally purposes, and consumption is more, is worth bigger.
Nitric acid is added to adjust the pH of filtrate according to the present invention, in step (3).Using the pH of nitre acid-conditioning solution, can keep away
Exempt to bring other impurity anions into.
According to the present invention, before micro-nano bubble generator is passed through, the pH of the filtrate that step (2) is obtained is adjusted to 5-
7, can for example adjust to the specific point value between 5,5.5,6,6.5 or 7, and above-mentioned numerical value, as space is limited and for simplicity
Consideration, the present invention specific point value that no longer scope described in exclusive list includes.
According to the present invention, step (3) is described to be adjusted the pH of filtrate the concrete operations to 5-7 and is：By in filtrate receiver
Filtrate is passed through from the water inlet of micro-nano bubble generator, while being passed through oxygen rich gas from air inlet, filtrate is in micro-nano gas
It is soaked after being aerated in generating apparatus and enters filtrate receiver from delivery port, then repeats, until the NO in filtrate2 -It is oxidized to completely
NO3 -Untill.
According to the present invention, the air inflow of the micro-nano bubble generator is 20- with the volume mass ratio of liquid inlet volume
100, for example can be the specific point value between 20,30,40,50,60,70,80,90 or 100, and above-mentioned numerical value, it is limited to a piece
Width and the consideration for simplicity, the present invention specific point value that no longer scope described in exclusive list includes.
Above-mentioned volume mass than referring to the ratio between air inflow (volume) and liquid inlet volume (quality) of micro-nano bubble generator,
Unit is L/t.
According to the present invention, the filtrate is passed through the amount of micro-nano bubble generator and the volume ratio of filtrate total amount per hour
It is 1:(1-2), for example, can be 1:1、1:1.1、1:1.2、1:1.3、1:1.4、1:1.5、1:1.6、1:1.7、1:1.8、1:1.9
Or 1:Specific point value between 2, and above-mentioned numerical value, as space is limited and for concise consideration, the present invention no longer exclusive list
The specific point value that the scope includes.
Aeration of the present invention refers to the process of to force the oxygen in air to be shifted in filtrate.
According to the present invention, the time of the aeration is 0.5-5h, for example can be 0.5h, 1h, 1.5h, 2h, 2.5h, 3h,
Specific point value between 3.5h, 4h, 4.5h or 5h, and above-mentioned numerical value, as space is limited and for concise consideration, the present invention is not
The specific point value that scope described in exclusive list includes again.
According to the present invention, the oxygen content of the oxygen rich gas is 20-100%, for example can be 20%, 30%, 40%,
50%th, the specific point value between 60%, 70%, 80%, 90% or 100%, and above-mentioned numerical value, as space is limited and for simplicity
Consideration, the present invention specific point value that no longer scope described in exclusive list includes.
The present invention does not limit the concrete composition of the oxygen rich gas, as long as being in above range by the control of its oxygen content
Can, exemplary, the oxygen rich gas can be air, oxygen or air and the gaseous mixture of other gases etc., but non-be only limitted to
This.
According to the present invention, to the hydrogen peroxide that 0-10wt% is added in the micro-nano bubble generator, nitrous acid is helped
Root is faster more fully oxidized to nitrate anion.The 0-10wt% refers to the 0-10wt% of filtrate total amount.The mode of the addition
Can be directly added in micro-nano bubble generator by water inlet, it is also possible to be added directly into the filtrate.
According to the present invention, the concentration of liquid is 30-60wt% after step (4) described evaporation and concentration, for example, can be
Specific point value between 30wt%, 35wt%, 40wt%, 45wt%, 50wt%, 55wt% or 60wt%, and above-mentioned numerical value,
As space is limited and for concise consideration, the present invention specific point value that no longer scope described in exclusive list includes.
According to the present invention, the temperature of step (4) described crystallization is 0-30 DEG C, for example can be 0 DEG C, 5 DEG C, 10 DEG C, 15 DEG C,
Specific point value between 20 DEG C, 25 DEG C or 30 DEG C, and above-mentioned numerical value, as space is limited and for concise consideration, the present invention is not
The specific point value that scope described in exclusive list includes again.
According to the present invention, step (4) the dry temperature is 10-30 DEG C, for example can be 10 DEG C, 15 DEG C, 20 DEG C, 25
DEG C or the specific point value between 30 DEG C, and above-mentioned numerical value, as space is limited and for concise consideration, the present invention no longer limit row
Lift the specific point value that the scope includes.
It is of the present invention that slag is given up as absorbent combined desulfurization and denitrification process generation as preferred technical scheme
The method of liquid recycling is comprised the following steps：
(1) waste liquid produced after using slag as absorbent combined desulfurization and denitration is carried out into separation of solid and liquid；The waste liquid
PH is 4-7, and the total concentration of the salt for containing is 10-60wt%, and the content of slag is 1-30wt%；
(2) it is 9-13 to quick lime and/or white lime regulation pH is added in the liquid obtained after step (1) separation of solid and liquid,
The completely rear filtering of precipitation；
(3) it is 5-7 that nitre acid for adjusting pH is added in the filtrate for obtaining to step (2), by the filtrate in filtrate receiver from micro-nano
The water inlet of bubble generator is passed through, while being passed through the oxygen rich gas that oxygen content is 20-100% from air inlet, filtrate is micro-
Enter filtrate receiver from delivery port after being aerated 0.5-5h in nano-bubble generating apparatus, then repeat, until the NO in filtrate2 -
NO is oxidized to completely3 -Untill；Wherein, the air inflow of the micro-nano bubble generator is with the volume mass ratio of liquid inlet volume
20-100, the volume ratio of amount and filtrate total amount that the filtrate is passed through micro-nano bubble generator per hour is 1:(1-2), to
The hydrogen peroxide of 0-10wt% is added in micro-nano bubble generator；
(4) after the liquid evaporation obtained after step (3) is aoxidized is concentrated into 30-60wt%, crystallized at 0-30 DEG C, mistake
Filter, the crystal that will be filtrated to get is dried at 10-30 DEG C, obtains nitric acid calcium product.
Compared with prior art, the present invention at least has the advantages that：
The present invention solve slag as during absorbent combined desulfurization and denitrification process produce waste liquid easily cause it is secondary
The problem of pollution, nitrate is fully converted to by nitrite, realize in waste liquid N element all of having obtained pure
Net nitric acid calcium product, the product reaches industrial calcium nitrate and agricultural calcium nitrate national standard simultaneously, with good economy
Benefit and wide industrial applications prospect.
Specific embodiment
For the present invention is better described, technical scheme is readily appreciated, below to the present invention further specifically
It is bright.But following embodiments is only simple example of the invention, the scope of the present invention is not represented or limits, this
Invention protection domain is defined by claims.
Specific embodiment of the invention part provides and a kind of slag is produced as absorbent combined desulfurization and denitrification process
The method of devil liquor recovery treatment, the preparation method comprises the following steps：
(1) waste liquid that slag is produced as absorbent combined desulfurization and denitrification process is carried out into separation of solid and liquid；
(2) removed to addition quick lime in the liquid obtained after step (1) separation of solid and liquid and/or white lime regulation pH
It is miscellaneous, the completely rear filtering of precipitation；
(3) pH of the filtrate for obtaining step (2) is adjusted to 5-7, then carries out oxygen by micro-nano bubble generator
Change；
(4) crystallized after the liquid evaporation concentration obtained after step (3) is aoxidized, filtering is dried, and obtains nitric acid calcium product.
Wherein, the pH of filtrate is adjusted into the concrete operations to 5-7 in step (3) is：By the filtrate in filtrate receiver from micro-
The water inlet of nano-bubble generating apparatus is passed through, while being passed through oxygen rich gas from air inlet, filtrate fills in micro-nano bubble
Enter filtrate receiver from delivery port after putting aeration, then repeat, until the NO in filtrate2 -NO is oxidized to completely3 -For
Only.
It is below present invention typical case but non-limiting example：
Embodiment 1
Steel slag slurry absorbs SO in the present embodiment2And NOxIn the waste liquid for producing afterwards the content of slag be 15wt%, pH=6,
Total salt concentration is 30wt%.
(1) waste liquid is filtered, is removed solid impurity；
(2) the filtrate quick lime regulation pH for obtaining step (1) is 9, and precipitation removes NO3 -、NO2 -And Ca2+Outside impurity
Ion, is filtrated to get filtrate；
(3) filtrate for obtaining step (2) plus nitre acid for adjusting pH are 6, then by the filtrate in filtrate receiver from micro-nano gas
The water inlet of generating apparatus of being soaked is passed through, and it is the 1/2 of filtrate total amount to control intake per hour, while total from water inlet addition filtrate
The hydrogen peroxide of quality 10%, air (oxygen content 21%) is passed through from air inlet, and air inflow is with the volume mass ratio of liquid inlet volume
50L/t, filtrate enters filtrate receiver after being aerated 3h in micro-nano bubble generator from delivery port, then repeats, until
NO in filtrate2 -NO is oxidized to completely3 -Untill；
(4) liquid obtained after step (3) is aoxidized is evaporated concentration, and the concentration of calcium nitrate is in concentrate
30wt%, then by concentrate in 5 DEG C of crystallizations, filtering, and dries at 10 DEG C, obtains pure nitric acid calcium product.The nitric acid
Calcium product reaches industrial calcium nitrate and agricultural calcium nitrate national standard.
Embodiment 2
Steel slag slurry absorbs SO in the present embodiment2And NOxThe content of slag is 10wt%, pH=in the waste liquid for producing afterwards
5.5, total salt concentration is 40wt%.
(1) waste liquid is filtered, is removed solid impurity；
(2) it is 10.8 that the filtrate for obtaining step (1) adjusts pH with CaO saturated solutions, and precipitation removes NO3 -、NO2 -And Ca2+It
Outer foreign ion, is filtrated to get filtrate；
(3) filtrate for obtaining step (2) plus nitric acid regulation pH=6.5, then by the filtrate in filtrate receiver from micro-nano
The water inlet of bubble generator is passed through, and it is the 0.8 of filtrate total amount to control intake per hour, while adding filtrate from water inlet
The hydrogen peroxide of gross mass 5%, air and oxygen mixed gas (oxygen content 30%), air inflow and liquid inlet volume are passed through from air inlet
Volume mass ratio is 30L/t, and filtrate enters filtrate receiver, Ran Houchong after being aerated 2h in micro-nano bubble generator from delivery port
Multiple operation, until the NO in filtrate2 -NO is oxidized to completely3 -Untill；
(4) liquid obtained after step (3) is aoxidized is evaporated concentration, and the concentration of calcium nitrate is in concentrate
60wt%, then by concentrate in 30 DEG C of crystallizations, filtering, and dries at 15 DEG C, obtains pure nitric acid calcium product.The nitric acid
Calcium product reaches industrial calcium nitrate and agricultural calcium nitrate national standard.
Embodiment 3
Steel slag slurry absorbs SO in the present embodiment2And NOxThe content of slag is 20wt%, pH=in the waste liquid for producing afterwards
6.5, total salt concentration is 35wt%.
(1) waste liquid is filtered, is removed solid impurity；
(2) the filtrate white lime regulation pH for obtaining step (1) is 10, and precipitation removes NO3 -、NO2 -And Ca2+Outside it is miscellaneous
Matter ion, is filtrated to get filtrate；
(3) filtrate for obtaining step (2) plus nitric acid regulation pH=6.7, then by the filtrate in filtrate receiver from micro-nano
The water inlet of bubble generator is passed through, and it is the 0.8 of filtrate total amount to control intake per hour, while adding filtrate from water inlet
The hydrogen peroxide of gross mass 4%, air and oxygen mixed gas (oxygen content 40%), air inflow and liquid inlet volume are passed through from air inlet
Volume mass ratio is 40L/t, and filtrate enters filtrate receiver after being aerated 2.5h in micro-nano bubble generator from delivery port, then
Repeat, until the NO in filtrate2 -NO is oxidized to completely3 -Untill；
(4) liquid obtained after step (3) is aoxidized is evaporated concentration, and the concentration of calcium nitrate is in concentrate
50wt%, then by concentrate in 15 DEG C of crystallizations, filtering, and dries at 30 DEG C, obtains pure nitric acid calcium product.The nitric acid
Calcium product reaches industrial calcium nitrate and agricultural calcium nitrate national standard.
Embodiment 4
Steel slag slurry absorbs SO in the present embodiment2And NOxThe content of slag is 25wt%, pH=in the waste liquid for producing afterwards
6.8, total salt concentration is 25wt%.
(1) waste liquid is filtered, is removed solid impurity；
(2) filtrate for obtaining step (1) is with Ca (OH)2Saturated solution regulation pH is 12, and precipitation removes NO3 -、NO2 -And Ca2+
Outside foreign ion, be filtrated to get filtrate；
(3) filtrate for obtaining step (2) plus nitric acid regulation pH=7, then by the filtrate in filtrate receiver from micro-nano gas
The water inlet of generating apparatus of being soaked is passed through, and it is the 0.9 of filtrate total amount to control intake per hour, while total from water inlet addition filtrate
The hydrogen peroxide of quality 2%, the body of air and oxygen mixed gas (oxygen content 60%), air inflow and liquid inlet volume is passed through from air inlet
Product mass ratio is 60L/t, and filtrate enters filtrate receiver, Ran Houchong after being aerated 3.5h in micro-nano bubble generator from delivery port
Multiple operation, until the NO in filtrate2 -NO is oxidized to completely3 -Untill；
(4) liquid obtained after step (3) is aoxidized is evaporated concentration, and the concentration of calcium nitrate is in concentrate
40wt%, then by concentrate in 10 DEG C of crystallizations, filtering, and dries at 15 DEG C, obtains pure nitric acid calcium product.The nitric acid
Calcium product reaches industrial calcium nitrate and agricultural calcium nitrate national standard.
Embodiment 5
Steel slag slurry absorbs SO in the present embodiment2And NOxThe content of slag is 30wt%, pH=in the waste liquid for producing afterwards
5.5, total salt concentration is 50wt%.
(1) waste liquid is filtered, is removed solid impurity；
(2) the filtrate quick lime regulation pH for obtaining step (1) is 13, and precipitation removes NO3 -、NO2 -And Ca2+Outside it is miscellaneous
Matter ion, is filtrated to get filtrate；
(3) filtrate for obtaining step (2) plus nitric acid regulation pH=5.8, then by the filtrate in filtrate receiver from micro-nano
The water inlet of bubble generator is passed through, and it is the 0.6 of filtrate total amount to control intake per hour, while adding filtrate from water inlet
The hydrogen peroxide of gross mass 6%, oxygen (oxygen content 100%) is passed through from air inlet, and air inflow is with the volume mass ratio of liquid inlet volume
80L/t, filtrate enters filtrate receiver after being aerated 1h in micro-nano bubble generator from delivery port, then repeats, until
NO in filtrate2 -NO is oxidized to completely3 -Untill；
(4) liquid obtained after step (3) is aoxidized is evaporated concentration, and the concentration of calcium nitrate is in concentrate
55wt%, then by concentrate in 25 DEG C of crystallizations, filtering, and dries at 14 DEG C, obtains pure nitric acid calcium product.The nitric acid
Calcium product reaches industrial calcium nitrate and agricultural calcium nitrate national standard.
Comparative example 1
Compared with Example 1, in addition to the quick lime in step (2) is replaced with into NaOH solution, other conditions with implement
Example 1 is identical.
Result shows：Introduce impurity Na+, there are a large amount of nitric acid sodium impurities in ion in the product of preparation.
Comparative example 2
Compared with Example 1, in addition to the pH in step (3) is adjusted into 4, other conditions are same as Example 1.
Result shows：NO2 -It is unstable, nitrate anion and NO are generated, produce pernicious gas.
Comparative example 3
Compared with Example 1, in addition to the pH in step (3) is adjusted into 8, other conditions are same as Example 1.
Result shows：It is identical with comparative example 2, it is impossible to completely by NO2 -It is oxidized to NO3 -, there is nitrous acid in the product of preparation
Calcium impurities.
Comparative example 4
Compared with Example 1, " filtrate that step (2) is obtained is heated to 40 DEG C, in oxygen except step (3) is replaced with
3h is processed under gas atmosphere " outward, other conditions are same as Example 1.
Result shows：Part calcium nitrite impurity is still present in the product of preparation, NO under these conditions is illustrated2 -Not
Complete oxidation is NO3 -。
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited in above-mentioned implementation method
Detail, in range of the technology design of the invention, various simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned specific embodiment, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy is no longer separately illustrated.
Additionally, can also be combined between a variety of implementation methods of the invention, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (10)
1. a kind of method that devil liquor recovery produced as absorbent combined desulfurization and denitrification process to slag is processed, its feature exists
In the described method comprises the following steps：
(1) waste liquid that slag is produced as absorbent combined desulfurization and denitrification process is carried out into separation of solid and liquid；
(2) removal of impurities is carried out to addition quick lime in the liquid obtained after step (1) separation of solid and liquid and/or white lime regulation pH, is sunk
Filtering after forming sediment completely；
(3) pH of the filtrate for obtaining step (2) is adjusted to 5-7, is then aoxidized by micro-nano bubble generator；
(4) crystallized after the liquid evaporation concentration obtained after step (3) is aoxidized, filtering is dried, and obtains nitric acid calcium product.
2. the method for claim 1, it is characterised in that the content of slag is 1-30wt% in step (1) described waste liquid.
3. method as claimed in claim 1 or 2, it is characterised in that contain NO in step (1) described waste liquid3 -And NO2 -；
Preferably, SO is contained in step (1) described waste liquid4 2-、SO3 2-、HSO4 -Or HSO3 -In at least one；
Preferably, Mg is contained in step (1) described waste liquid2+、Ca2+、Mn2+Or Fe3+In at least two；
Preferably, the pH of step (1) described waste liquid is 4-7；
Preferably, the total concentration of the salt that step (1) described waste liquid contains is 10-60wt%.
4. the method as described in claim any one of 1-3, it is characterised in that step (2) quick lime and/or white lime
Feed postition is thrown and/or wet throwing for dry.
5. the method as described in claim any one of 1-4, it is characterised in that quick lime and/or white lime are added in step (2)
PH to 9-13 is adjusted afterwards.
6. the method as described in claim any one of 1-5, it is characterised in that add nitric acid to adjust the pH of filtrate in step (3).
7. the method as described in claim any one of 1-6, it is characterised in that step (3) is described to adjust to 5-7 the pH of filtrate
Concrete operations afterwards are：Filtrate in filtrate receiver is passed through from the water inlet of micro-nano bubble generator, while from air inlet
Oxygen rich gas is passed through, filtrate enters filtrate receiver, then repeats after being aerated in micro-nano bubble generator from delivery port,
Until the NO in filtrate2 -NO is oxidized to completely3 -Untill.
8. the method as described in claim any one of 1-7, it is characterised in that the air inflow of the micro-nano bubble generator
It is 20-100 with the volume mass ratio of liquid inlet volume；
Preferably, the volume ratio of amount and filtrate total amount that the filtrate is passed through micro-nano bubble generator per hour is 1:(1-
2)；
Preferably, the time of the aeration is 0.5-5h；
Preferably, the oxygen content of the oxygen rich gas is 20-100%；
Preferably, to the hydrogen peroxide that 0-10wt% is added in the micro-nano bubble generator.
9. the method as described in claim any one of 1-8, it is characterised in that liquid is dense after step (4) described evaporation and concentration
It is 30-60wt% to spend；
Preferably, the temperature of step (4) described crystallization is 0-30 DEG C；
Preferably, step (4) the dry temperature is 10-30 DEG C.
10. the method as described in claim any one of 1-9, it is characterised in that the described method comprises the following steps：
(1) waste liquid produced after using slag as absorbent combined desulfurization and denitration is carried out into separation of solid and liquid；The pH of the waste liquid is
4-7, the total concentration of the salt for containing is 10-60wt%, and the content of slag is 1-30wt%；
(2) it is 9-13, precipitation to quick lime and/or white lime regulation pH is added in the liquid obtained after step (1) separation of solid and liquid
Filtering after completely；
(3) it is 5-7 that nitre acid for adjusting pH is added in the filtrate for obtaining to step (2), by the filtrate in filtrate receiver from micro-nano bubble
The water inlet of generating means is passed through, while being passed through the oxygen rich gas that oxygen content is 20-100% from air inlet, filtrate is micro-nano
Enter filtrate receiver from delivery port after being aerated 0.5-5h in bubble generator, then repeat, until the NO in filtrate2 -Completely
It is oxidized to NO3 -Untill；Wherein, the air inflow of the micro-nano bubble generator and the volume mass ratio of liquid inlet volume are 20-
100, the volume ratio of amount and filtrate total amount that the filtrate is passed through micro-nano bubble generator per hour is 1:(1-2), to institute
State the hydrogen peroxide of addition 0-10wt% in micro-nano bubble generator；
(4) after the liquid evaporation obtained after step (3) is aoxidized is concentrated into 30-60wt%, crystallized at 0-30 DEG C, filtering, will
The crystal being filtrated to get is dried at 10-30 DEG C, obtains nitric acid calcium product.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107857310A (en) * | 2017-11-02 | 2018-03-30 | 东南大学 | Desulphurization denitration waste liquid degradation treatment equipment |
| CN107973323A (en) * | 2017-12-06 | 2018-05-01 | 中国科学院过程工程研究所 | A kind of method for oxidation of desulphurization denitration waste liquid Nitrite ion |
| CN109110791A (en) * | 2018-09-26 | 2019-01-01 | 北京建筑材料科学研究总院有限公司 | The method for preparing high pure nitric acid calcium with desulphurization denitration by-product |
| CN110127641A (en) * | 2018-02-02 | 2019-08-16 | 中国科学院过程工程研究所 | A method of recycling nitrite from desulphurization denitration waste liquid |
| CN114249475A (en) * | 2020-09-22 | 2022-03-29 | 自然资源部天津海水淡化与综合利用研究所 | Recycling treatment method for wastewater containing benzotriazole, sodium nitrate, sodium nitrite and sodium chloride |
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| CN102806004A (en) * | 2011-05-30 | 2012-12-05 | 中国石油化工股份有限公司 | Magnesium desulfurization byproduct recovery process |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107857310A (en) * | 2017-11-02 | 2018-03-30 | 东南大学 | Desulphurization denitration waste liquid degradation treatment equipment |
| CN107973323A (en) * | 2017-12-06 | 2018-05-01 | 中国科学院过程工程研究所 | A kind of method for oxidation of desulphurization denitration waste liquid Nitrite ion |
| CN110127641A (en) * | 2018-02-02 | 2019-08-16 | 中国科学院过程工程研究所 | A method of recycling nitrite from desulphurization denitration waste liquid |
| CN109110791A (en) * | 2018-09-26 | 2019-01-01 | 北京建筑材料科学研究总院有限公司 | The method for preparing high pure nitric acid calcium with desulphurization denitration by-product |
| CN114249475A (en) * | 2020-09-22 | 2022-03-29 | 自然资源部天津海水淡化与综合利用研究所 | Recycling treatment method for wastewater containing benzotriazole, sodium nitrate, sodium nitrite and sodium chloride |
| CN114249475B (en) * | 2020-09-22 | 2023-09-19 | 自然资源部天津海水淡化与综合利用研究所 | Method for recycling wastewater containing benzotriazole, sodium nitrate, sodium nitrite and sodium chloride |
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