CN104108780B - Method of wastewater treatment in acrylonitrile process subtractive process - Google Patents
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Abstract
The present invention relates to the method for wastewater treatment in a kind of acrylonitrile process subtractive process, mainly there is complex treatment process during the waste water in solution process acrylonitrile process subtractive process, multi-effect evaporation system is frequently occluded, the problem creating the waste water residual liquid of high COD malicious, high after process.The present invention, by using the waste water produced during propylene or propane ammoxidation production acrylonitrile as raw material, passes through the wet oxidation reaction device equipped with catalyst after oxygen mix；Reaction temperature in described reactor is 200～320 DEG C, and pressure is 5～15MPa, and the time of staying is 5～120 minutes；Described catalyst includes following components: A in terms of parts by weight) the zirconia ceramics cystosepiment of 96～98 parts；Be loaded in B thereon) 2～4 parts of choosings preferably solve this problem to the technical scheme of at least one in Cu, Mn, Ce or Co metal-oxide, can be used for the waste water in acrylonitrile process subtractive process and process.
Description
Technical field
The present invention relates to a kind of method processing industry acrylonitrile refining waste water.
Background technology
Acrylonitrile is a kind of important Organic Chemicals, and general employing propylene or propane method for ammoxidation produce.Propylene
Or propane, ammonia and oxygen are by fluidized-bed reactor, generate acrylonitrile and by-product, enter back into recovery and refining system is isolated and purified
Acrylonitrile (USP3936360).Admixture of gas after the reaction exists some unreacted ammonia, therefore, for ensureing acrylonitrile
Quality, it is necessary to remove ammonia.United States Patent (USP) USP3649179 and USP3936360 use sulphuric acid, hydrochloric acid, phosphoric acid or nitric acid to remove
Unreacted ammonia.The method mostly using sulphuric acid and ammonia to react generation ammonium sulfate in China's acrylonitrile commercial production removes ammonia, generation
Ammonium sulfate is by being recycled as chemical fertilizer, and mother solution then enters incinerator and burns.Owing to ammonium sulfate solution containing substantial amounts of poisonous and harmful
Material, as containing cyanogen compound, azacyclo-etc., the sulfur ammonium of recovery is used as chemical fertilizer can pollute soil.Meanwhile, mother solution burns
Need to fill great amount of fuel oil, energy consumption is high, and burning process releases SO simultaneously2, NO2Deng gas, environment is caused secondary pollution.Therefore, open
Send out a kind of for high salt, the method for wastewater treatment of high content of organics, make the acrylic nitrile waste water after process reach device recycle-water
Standard, effectively reduce acrylonitrile installation pollutant discharge amount and energy consumption, it is achieved the greenization running of device seems particularly necessary.
Wet oxidation is a kind of technology processing organic wastewater grown up the 1950's.This method is at high temperature
Under the conditions of (125～320 DEG C), high pressure (0.5～20MPa), with air or pure oxygen as oxidant, in the liquid phase by organic pollution
It is oxidized to CO2With inorganic matter or the chemical processes of small organic molecule such as water.During wet oxidation reaction, add catalyst
Wet oxidation efficiency can be effectively improved, reduce reaction condition.This energy saving technology environmental protection, can process poisonous, harmful, high concentration is organic
Waste water, thus it is applicable to process the acrylic nitrile waste water of sulfur-bearing ammonium.CN1394818 discloses a kind of for processing industry containing high-sulfur
Amount, the method for organic wastewater of high concentration.But the method needs to be diluted waste water, and method relates to wet oxidation and electricity is many
Being catalyzed oxidation, complex process mutually, operating cost is high.After multiple techniques processes, COD total removal rate reaches 89.2～92.3%.This
Inventing by using heterogeneous catalyst, in fixed bed reactors, reaction temperature controls at 200～300 DEG C, oxygen or air pressure
Power, under 5～10MPa, makes the industrial acrylic nitrile waste water of the most diluted sulfur-bearing ammonium, carrier gas and catalyst three be fully contacted 10
～120min, after reaction, the organic cod content in waste water can reduce by 90.8%.The process route that the method relates to is simple, is suitable for
Process the industrial acrylic nitrile waste water of sulfur-bearing ammonium.
Summary of the invention
The technical problem to be solved exists when being and process acrylonitrile process refining system waste water in conventional art
Complex treatment process, multi-effect evaporation system is frequently occluded, the problem creating the waste water residual liquid of high COD malicious, high after process, it is provided that
A kind of method of wastewater treatment in new acrylonitrile process subtractive process.The method has that process route is simple, equipment takes up an area face
Long-pending little, energy consumption is low and can the most effectively reduce the advantage of organic cod content in waste water.
For solving above-mentioned technical problem, the present invention adopts the following technical scheme that in a kind of acrylonitrile process subtractive process
Method of wastewater treatment, produce the waste water produced during acrylonitrile as raw material with propylene or propane ammoxidation, with oxygen mix
Afterwards by the wet oxidation reaction device equipped with catalyst；Reaction temperature in described reactor is 200～320 DEG C, pressure be 5～
15MPa, the time of staying is 5～120 minutes；Described catalyst includes following components: A in terms of parts by weight) oxygen of 96～98 parts
Change zircon ceramic cystosepiment；Be loaded in B thereon) 2～4 parts of choosings are at least one in Cu, Mn, Ce or Co metal-oxide.
In technique scheme, the waste water produced in acrylonitrile refining preferably passes through wet oxidation with after oxygen mix
Reactor；The consumption of oxygen is preferably and calculates 1～1.4 times of requisite oxygen tolerance by original waste water COD value, more preferably 1.2～
1.3 again；Reaction temperature in reactor is preferably 220～290 DEG C, and pressure is preferably 5～10MPa, and the time of staying is preferably 10
～90 minutes.
In technique scheme, catalyst preferably includes following components: A in terms of parts by weight) zirconium oxide of 96～97 parts
Ceramic foam plate；Be loaded in B thereon) 3～4 parts of choosings are at least one in Cu, Mn, Ce or Co metal-oxide.
In technique scheme, the preparation method of catalyst comprises the steps: 1) zirconia ceramic cystosepiment is soaked
Stain is at least one saline solution in Cu, Mn, Ce or Co, and dipping temperature is 20～100 DEG C, and dip time is 12～24
Hour, it is dried to obtain catalyst precursor afterwards；2) catalyst precursor roasting 1 under the conditions of 200～800 DEG C in air atmosphere
～10 hours, obtain catalyst prod.Wherein, step 1) in dipping temperature be preferably 40～80 DEG C, dip time is preferably 8
～18 hours；Step 2) in sintering temperature be preferably 300～700 DEG C, roasting time is preferably 2～8 hours.
It is catalyst carrier that the present invention chooses zirconia ceramic cystosepiment, make use of its higher hydrothermal stability and height
The characteristic of voidage, can make organic wastewater be fully contacted with the catalyst of preparation, improve the reaction efficiency of wet oxidation.
Using technical scheme, result shows to use weight proportion ZrO2:CuO:MnO2:CeO2:CoO2It is 96:
The catalyst of 1.5:1:1:0.5, is 270 DEG C in reaction temperature, and pressure is 8.5MPa, and the time of staying is 40 minutes, the use of oxygen
Under conditions of amount is 1.4 times by original waste water COD value calculating requisite oxygen tolerance, catalyst can effectively reduce industry acrylonitrile essence
The content of organics of spent process water processed, reaches 98.8% through wet oxidation processed waste water COD value clearance, achieves preferably
Technique effect.
Below by embodiment, the invention will be further elaborated, but these embodiments are in no case to this
Bright scope is construed as limiting.
Detailed description of the invention
[embodiment 1]
With industry acrylonitrile refining waste water as raw material, the COD value of waste water is 48600mg/L.Waste water and oxygen mix
Afterwards by being filled with the 125mL wet oxidation reaction device of 120g catalyst WAO-01.Reaction temperature in reactor is 220 DEG C,
Pressure is 5MPa, and the time of staying is 120 minutes, and the consumption of oxygen is to calculate the 1.15 of requisite oxygen tolerance by original waste water COD value
Times.Reaction result is shown in Table 1.
Used catalyst WAO-01 in terms of weight proportion, ZrO2:CuO:MnO2:CeO2:CoO2For 98:2:0:0:0.Catalysis
The preparation method of agent is: 1) by 117.6g zirconia ceramic cystosepiment incipient impregnation in containing 7.3g Cu (NO3)2·3H2O
Aqueous solution in, dipping temperature is 20 DEG C, and dip time is 24 hours, is dried to obtain catalyst precursor afterwards；2) catalyst
Presoma roasting 10 hours under the conditions of 300 DEG C in atmosphere, obtain catalyst WAO-01.Formula and the preparation condition of catalyst are shown in
Table 2.
[embodiment 2]
With industry acrylonitrile refining waste water as raw material, the COD value of waste water is 12680mg/L.Waste water and oxygen mix
Afterwards by being filled with the 125mL wet oxidation reaction device of 120g catalyst WAO-02.Reaction temperature in reactor is 250 DEG C,
Pressure is 7MPa, and the time of staying is 85 minutes, and the consumption of oxygen is calculate requisite oxygen tolerance by original waste water COD value 1.0 times.
Reaction result is shown in Table 1.
Used catalyst WAO-01 in terms of weight proportion, ZrO2:CuO:MnO2:CeO2:CoO2For 98:0:2:0:0.Catalysis
The preparation method of agent is: 1) by 117.6g zirconia ceramic cystosepiment incipient impregnation in containing 7.9g Mn (NO3)2·3H2O
Aqueous solution in, dipping temperature is 60 DEG C, and dip time is 12 hours, is dried to obtain catalyst precursor afterwards；2) catalyst
Presoma roasting 8 hours under the conditions of 350 DEG C in atmosphere, obtain catalyst WAO-02.Formula and the preparation condition of catalyst are shown in
Table 2.
[embodiment 3]
With industry acrylonitrile refining waste water as raw material, the COD value of waste water is 17500mg/L.Waste water and oxygen mix
Afterwards by being filled with the 125mL wet oxidation reaction device of 120g catalyst WAO-03.Reaction temperature in reactor is 240 DEG C,
Pressure is 6.5MPa, and the time of staying is 90 minutes, and the consumption of oxygen is to calculate the 1.1 of requisite oxygen tolerance by original waste water COD value
Times.Reaction result is shown in Table 1.
Used catalyst WAO-01 in terms of weight proportion, ZrO2:CuO:MnO2:CeO2:CoO2For 97:0:0:3:0.Catalysis
The preparation method of agent is: 1) by 116.4g zirconia ceramic cystosepiment incipient impregnation in containing 9.1g Ce (NO3)3·6H2O
Aqueous solution in, dipping temperature is 80 DEG C, and dip time is 10 hours, is dried to obtain catalyst precursor afterwards；2) catalyst
Presoma roasting 4 hours under the conditions of 500 DEG C in atmosphere, obtain catalyst WAO-03.Formula and the preparation condition of catalyst are shown in
Table 2.
[embodiment 4]
With industry acrylonitrile refining waste water as raw material, the COD value of waste water is 28800mg/L.Waste water and oxygen mix
Afterwards by being filled with the 125mL wet oxidation reaction device of 120g catalyst WAO-04.Reaction temperature in reactor is 290 DEG C,
Pressure is 10MPa, and the time of staying is 10 minutes, and the consumption of oxygen is to calculate the 1.05 of requisite oxygen tolerance by original waste water COD value
Times.Reaction result is shown in Table 1.
Used catalyst WAO-01 in terms of weight proportion, ZrO2:CuO:MnO2:CeO2:CoO2For 96:0:0:0:4.Catalysis
The preparation method of agent is: 1) by 115.2g zirconia ceramic cystosepiment incipient impregnation in containing 9.7g Co (NO3)2·6H2O
Aqueous solution in, dipping temperature is 60 DEG C, and dip time is 16 hours, is dried to obtain catalyst precursor afterwards；2) catalyst
Presoma roasting 6 hours under the conditions of 400 DEG C in atmosphere, obtain catalyst WAO-04.Formula and the preparation condition of catalyst are shown in
Table 2.
[embodiment 5]
With industry acrylonitrile refining waste water as raw material, the COD value of waste water is 48600mg/L.Waste water and oxygen mix
Afterwards by being filled with the 125mL wet oxidation reaction device of 120g catalyst WAO-05.Reaction temperature in reactor is 280 DEG C,
Pressure is 9.5MPa, and the time of staying is 20 minutes, and the consumption of oxygen is to calculate the 1.2 of requisite oxygen tolerance by original waste water COD value
Times.Reaction result is shown in Table 1.
Used catalyst WAO-01 in terms of weight proportion, ZrO2:CuO:MnO2:CeO2:CoO2For 97:2:1:0:0.Catalysis
The preparation method of agent is: 1) by 116.4g zirconia ceramic cystosepiment incipient impregnation in containing 7.3g Cu (NO3)2·3H2O
With 4.0g Mn (NO3)2·3H2In the aqueous solution of O, dipping temperature is 60 DEG C, and dip time is 18 hours, is dried to obtain afterwards and urges
Agent presoma；2) catalyst precursor roasting 3 hours under the conditions of 650 DEG C in atmosphere, obtain catalyst WAO-05.Catalyst
Formula and preparation condition be shown in Table 2.
[embodiment 6]
With industry acrylonitrile refining waste water as raw material, the COD value of waste water is 12680mg/L.Waste water and oxygen mix
Afterwards by being filled with the 125mL wet oxidation reaction device of 120g catalyst WAO-06.Reaction temperature in reactor is 260 DEG C,
Pressure is 8MPa, and the time of staying is 55 minutes, and the consumption of oxygen is calculate requisite oxygen tolerance by original waste water COD value 1.3 times.
Reaction result is shown in Table 1.
Used catalyst WAO-01 in terms of weight proportion, ZrO2:CuO:MnO2:CeO2:CoO2For 97:0:1:2:0.Catalysis
The preparation method of agent is: 1) by 116.4g zirconia ceramic cystosepiment incipient impregnation in containing 4.0g Mn (NO3)2·6H2O
With 6.1g Ce (NO3)3·6H2In the aqueous solution of O, dipping temperature is 100 DEG C, and dip time is 8 hours, is dried to obtain afterwards and urges
Agent presoma；2) catalyst precursor roasting 2 hours under the conditions of 700 DEG C in atmosphere, obtain catalyst WAO-06.Catalyst
Formula and preparation condition be shown in Table 2.
[embodiment 7]
With industry acrylonitrile refining waste water as raw material, the COD value of waste water is 28800mg/L.Waste water and oxygen mix
Afterwards by being filled with the 125mL wet oxidation reaction device of 120g catalyst WAO-07.Reaction temperature in reactor is 270 DEG C,
Pressure is 8.5MPa, and the time of staying is 40 minutes, and the consumption of oxygen is to calculate the 1.4 of requisite oxygen tolerance by original waste water COD value
Times.Reaction result is shown in Table 1.
Used catalyst WAO-01 in terms of weight proportion, ZrO2:CuO:MnO2:CeO2:CoO2For 96:1.5:1:1:0.5.
The preparation method of catalyst is: 1) by 115.2g zirconia ceramic cystosepiment incipient impregnation in containing 5.5g Cu (NO3)2·
3H2O、4.0g Mn(NO3)2·6H2O、3.0g Ce(NO3)3·6H2O and 1.2g Co (NO3)2·6H2In the aqueous solution of O, leaching
Stain temperature is 80 DEG C, and dip time is 12 hours, is dried to obtain catalyst precursor afterwards；2) catalyst precursor is in atmosphere
Roasting 4 hours under the conditions of 550 DEG C, obtain catalyst WAO-07.Formula and the preparation condition of catalyst are shown in Table 2.
[embodiment 8]
With industry acrylonitrile refining waste water as raw material, the COD value of waste water is 28800mg/L.Waste water and oxygen mix
Afterwards by being filled with the 125mL wet oxidation reaction device of 120g catalyst WAO-08.Reaction temperature in reactor is 280 DEG C,
Pressure is 9.5MPa, and the time of staying is 25 minutes, and the consumption of oxygen is to calculate the 1.25 of requisite oxygen tolerance by original waste water COD value
Times.Reaction result is shown in Table 1.
Used catalyst WAO-01 in terms of weight proportion, ZrO2:CuO:MnO2:CeO2:CoO2For 96:2:0:1:1.Catalysis
The preparation method of agent is: 1) by 115.2g zirconia ceramic cystosepiment incipient impregnation in containing 7.3g Cu (NO3)2·
3H2O、3.0g Ce(NO3)3·6H2O and 2.4g Co (NO3)2·6H2In the aqueous solution of O, dipping temperature is 70 DEG C, during dipping
Between be 16 hours, be dried to obtain catalyst precursor afterwards；2) catalyst precursor in atmosphere under the conditions of 600 DEG C roasting 3 little
Time, obtain catalyst WAO-08.Formula and the preparation condition of catalyst are shown in Table 2.
[embodiment 9]
With industry acrylonitrile refining waste water as raw material, the COD value of waste water is 48600mg/L.Waste water and oxygen mix
Afterwards by being filled with the 125mL wet oxidation reaction device of 120g catalyst WAO-09.Reaction temperature in reactor is 265 DEG C,
Pressure is 8MPa, and the time of staying is 60 minutes, and the consumption of oxygen is to calculate the 1.35 of requisite oxygen tolerance by original waste water COD value
Times.Reaction result is shown in Table 1.
Used catalyst WAO-01 in terms of weight proportion, ZrO2:CuO:MnO2:CeO2:CoO2For 96:0:1:2:1.Catalysis
The preparation method of agent is: 1) by 115.2g zirconia ceramic cystosepiment incipient impregnation in containing 4.0g Mn (NO3)2·
6H2O、6.1g Ce(NO3)3·6H2O and 2.4g Co (NO3)2·6H2In the aqueous solution of O, dipping temperature is 80 DEG C, during dipping
Between be 12 hours, be dried to obtain catalyst precursor afterwards；2) catalyst precursor in atmosphere under the conditions of 500 DEG C roasting 5 little
Time, obtain catalyst WAO-09.Formula and the preparation condition of catalyst are shown in Table 2.
[comparative example 1]
The waste water of acrylonitrile process refining system, by distillation, evaporates the waste water accounting for gross weight 80%, the waste water evaporated
Strip through stripper again.After analyzing the front waste water of evaporation and stripping, the COD value of waste water, the results are shown in Table 1.
Table 1
Table 2
Claims (8)
1. the method for wastewater treatment in acrylonitrile process subtractive process, produces acrylonitrile with propylene or propane ammoxidation and refines
During the waste water that produces be by the wet oxidation reaction device equipped with catalyst after raw material, with oxygen mix；Described reactor
In reaction temperature be 200～320 DEG C, pressure is 5～15MPa, and the time of staying is 5～120 minutes；Described catalyst is with weight
Number meter includes following components: A) the zirconia ceramics cystosepiment of 96～98 parts；Be loaded in B thereon) 2～4 parts selected from Cu,
Mn, Ce, Co or Cu-Mn, or Mn-Ce, or Cu-Ce-Co, or Mn-Ce-Co, or the metal-oxide of Cu-Mn-Ce-Co；Wherein,
The consumption of oxygen is calculate requisite oxygen tolerance by original waste water COD value 1～1.4 times.
Method of wastewater treatment in acrylonitrile process subtractive process the most according to claim 1, it is characterised in that described oxygen
Consumption be to calculate 1.2～1.3 times of requisite oxygen tolerance by original waste water COD value.
Method of wastewater treatment in acrylonitrile process subtractive process the most according to claim 1, it is characterised in that described reaction
Reaction temperature in device is 220～290 DEG C.
Method of wastewater treatment in acrylonitrile process subtractive process the most according to claim 1, it is characterised in that described reaction
Pressure in device is 5～10MPa.
Method of wastewater treatment in acrylonitrile process subtractive process the most according to claim 1, it is characterised in that described reaction
The time of staying in device is 10～90 minutes.
Method of wastewater treatment in acrylonitrile process subtractive process the most according to claim 1, it is characterised in that described catalysis
Agent includes following components: A in terms of parts by weight) the zirconia ceramics cystosepiment of 96～97 parts；Be loaded in B thereon) 3～4 parts
Selected from Cu, Mn, Ce, Co, or Cu and Mn, or Mn and Ce, or Cu and Ce and Co, or Mn and Ce and Co, or Cu and Mn and Ce and Co
Metal-oxide.
Method of wastewater treatment in acrylonitrile process subtractive process the most according to claim 1, it is characterised in that described catalysis
The preparation method of agent comprises the steps:
1) be impregnated in by zirconia ceramics cystosepiment at least one saline solution in Cu, Mn, Ce or Co, dipping temperature is
20～100 DEG C, dip time is 12～24 hours, is dried to obtain catalyst precursor afterwards；
2) catalyst precursor roasting 1～10 hours under the conditions of 200～800 DEG C in air atmosphere, obtain catalyst prod.
Method of wastewater treatment in acrylonitrile process subtractive process the most according to claim 7, it is characterised in that step 1) in
Dipping temperature be 40～80 DEG C, dip time is 8～18 hours；Step 2) in sintering temperature be 300～700 DEG C, roasting
Time is 2～8 hours.
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| CN105600909B (en) * | 2014-11-20 | 2019-06-11 | 中国石油化工股份有限公司 | The method of catalytic wet oxidation processing organic wastewater |
| CN108069495A (en) * | 2016-11-11 | 2018-05-25 | 中国石油化工股份有限公司抚顺石油化工研究院 | A kind of catalytic wet oxidation processing method of organic wastewater |
| KR20200088816A (en) * | 2017-11-23 | 2020-07-23 | 쉘 인터내셔날 리써취 마트샤피지 비.브이. | Wastewater treatment method |
| CN111115789B (en) * | 2018-10-30 | 2023-04-07 | 中国石油化工股份有限公司 | Method for treating refined waste water in acrylonitrile production process |
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| JPH04166228A (en) * | 1990-09-28 | 1992-06-12 | Mitsubishi Heavy Ind Ltd | Oxidation catalyst |
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| CN102040274A (en) * | 2009-10-13 | 2011-05-04 | 中国石油化工股份有限公司 | Catalysis wet-type oxidation treatment method for sulfur-containing wastewater |
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