CN111672317B - Purification treatment method for distillation still residue - Google Patents
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- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
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- B01J29/146—Y-type faujasite
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- B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
- B01J29/185—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
- B01J29/20—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type containing iron group metals, noble metals or copper
- B01J29/24—Iron group metals or copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
Abstract
The invention discloses a purification treatment method of rectifying still residues, which comprises the following steps: the temporary oxygen cracking device is in a continuous rotating state, after the rectifying still residue enters the temporary oxygen cracking device, low-temperature temporary oxygen cracking oxidation treatment is carried out in the air atmosphere and in the presence of a temporary oxygen cracking catalyst, and gas containing organic matters generated by cracking oxidation treatment enters the catalytic oxidation device for catalytic oxidation treatment. The invention is suitable for kettle residues with the boiling point or sublimation point of oxide formed by any element in any rectification kettle residue after the temporary oxygen cracking being not higher than 400 ℃, realizes the treatment of the rectification kettle residue at the temperature of not more than 550 ℃ by utilizing the dual-function temporary oxygen cracking catalyst with cracking and oxidation, avoids the defects of large fuel consumption and high treatment temperature in the traditional method, and simultaneously avoids the possibility of secondary pollution caused by VOC-containing flue gas generated by high-temperature burning in the traditional method.
Description
Technical Field
The invention belongs to the field of environmental protection and chemical waste comprehensive treatment and utilization, and particularly relates to a purification treatment method for rectifying still residues.
Background
Various distillation kettle residues are inevitably generated in the chemical process industry, are difficult to treat, have the characteristics of complex composition, toxicity, harm and great environmental hazard, and become tripfoot stones for the sustainable development of enterprises. In the face of increasingly strict environmental protection policies, the treatment and disposal of the distillation still residue become problems to be solved urgently.
Patent CN106902489A discloses a method for treating CTC distillation still residue, which comprises removing impurities in the distillation still residue by using an alcohol solvent, adding solid alkali in batches for alcoholysis, converting chlorine-containing pyridine compounds into chlorine-free compounds, adding acid after alcoholysis to adjust the pH value to 4-6, washing with water for multiple times, collecting an organic phase, and burning. The adopted alcohol solvent is methanol, ethanol, butanol or isopropanol, and the addition amount is at least 1-10 times of the weight of the kettle residue. After alcoholysis, hydrochloric acid, phosphoric acid or dilute sulfuric acid is also needed for neutralization, so that acid is consumed while alkali is consumed, and the treatment cost is increased.
Patent CN103613242A discloses a synthetic leather distillation still residue resource comprehensive utilization method, which comprises diluting the distillation still residue, performing biochemical treatment with compound microorganism bacteria, and fermenting to generate biogas. However, since the biological bacteria limit the COD concentration in the treated water, a large amount of water is needed to dilute the kettle residue to a COD value of 5000-10000 mg/L in the water when the kettle residue is treated, otherwise the microorganism bacteria are killed by poison. The method requires a large amount of water for dilution, and the treatment cost is high.
Plum blossom law and the like[1]The method for treating organic fluorine residual liquid by adopting an incineration method needs to add hydrogen as fuel in the treatment process, and the combustion temperature is up to over 1000 ℃. The method not only needs fuel, but also has the treatment temperature of over 1000 ℃, and has extremely strict requirements on the material of the incinerator.
Reference documents:
[1] li Sheng method, Zheng Hui Min, Chen Xin kang, incineration treatment of organic fluorine raffinate, chemical environmental protection, 1983, 3(1): 19-22.
Disclosure of Invention
Aiming at the defects of large water consumption, fuel consumption or overhigh treatment temperature of the existing kettle residue treatment method, the invention aims to provide a low-cost method for treating the rectification kettle residue at low temperature.
The purpose of the invention is realized by the following technical scheme:
a purification treatment method of distillation still residue comprises the following steps: the near oxygen cracking device is in a continuous rotating state, after the rectifying still residue enters the near oxygen cracking device, low-temperature near oxygen cracking oxidation treatment is carried out in the air atmosphere and in the presence of a near oxygen cracking catalyst, and gas containing organic matters generated by the cracking oxidation treatment enters the catalytic oxidation device for catalytic oxidation treatment, so that secondary pollution is deeply purified and eliminated.
The average molecular weight of the rectifying still residue is not less than 10000kg/kmol, and the boiling point or sublimation point of an oxide formed by any element in the rectifying still residue after the oxygen cracking is not higher than 400 ℃; generally, the residue of the rectifying still is formed by combining any element of carbon, hydrogen, oxygen, nitrogen, sulfur, phosphorus, chlorine, bromine, fluorine and iodine; preferably, the distillation residue kettle is formed by combining carbon, hydrogen, oxygen and/or at least one element selected from nitrogen, sulfur, phosphorus, chlorine, bromine, fluorine and iodine.
The rectifying still is the rectifying still residue produced in the refining process of tert-butyl acrylate, the rectifying still residue produced in the refining process of n-butyl acetate, the rectifying still residue produced in the refining process of tert-butyl acetate, the rectifying still residue produced in the process of producing benzaldehyde by a toluene chlorination hydrolysis method, the rectifying still residue produced in the refining process of glyphosate, the rectifying still residue produced in the production process of nicosulfuron, and the rectifying still residue produced in the refining process of aniline products.
The distillation still residue accounts for 0.5-1 tonResidual kettle/(ton)Catalyst and process for preparing sameH) entering the temporary oxygen cracking device at a speed of ensuring that the rectification kettle residue is completely embedded by the rolling catalyst and simultaneously is 15000-25000 m3/(ton)Residual kettleH) air is introduced at a rate.
The temporary oxygen cracking catalyst is prepared by loading an oxide with alkalinity and an oxide with oxidability on a carrier. The preparation method of the catalyst is a conventional impregnation method. The particle size of the temporary oxygen cracking catalyst is 1-200 microns. The alkaline oxide is helpful for cracking reaction of macromolecule rectifying still residue, and plays an auxiliary role on the oxidative oxide, and the oxidative oxide is not only helpful for oxidizing cracking molecules into inorganic micromolecular substances such as carbon dioxide, water and the like under oxygen atmosphere, but also has a cracking function on rectifying still residue, and has double functions. The adoption of the powder catalyst is beneficial to reducing the particle volume of the catalyst, increasing the contact area with the residual materials of the rectifying still and improving the reaction effect.
The oxide with alkalinity is one of calcium oxide, magnesium oxide, beryllium oxide or barium oxide, and the load capacity is 1-5 wt%; the oxide with oxidability is one of copper oxide, chromium oxide, vanadium oxide, titanium oxide, cerium oxide, manganese oxide and cobalt oxide, and the load amount is 5-25 wt%; the carrier is alumina, HY molecular sieve or mordenite.
The temperature of the oxygen cracking oxidation treatment is 450-550 ℃.
The outlet of the temporary oxygen cracking device containsThe content of organic matters in the organic matter gas is 500-5000 mg/m3。
The gas containing organic matters is used for 10000-30000 h-1The volume space velocity of the gas enters a catalytic oxidation device, the temperature of catalytic oxidation treatment is 250-450 ℃, and the content of organic matters in the outlet gas of the catalytic oxidation device is 0-50 mg/m3。
The catalyst used in the catalytic oxidation treatment is mechanically molded with a temporary oxygen cracking catalyst or a commercially available catalytic combustion catalyst.
The catalytic combustion catalyst can be a commercial honeycomb KND-691 or KND-561 noble metal catalyst.
A system for rectifying still residue purification treatment comprises an oxygen-adjacent cracking device and a catalytic oxidation device which are sequentially connected in series, wherein the same end of the oxygen-adjacent cracking device is respectively provided with a rectifying still residue inlet and an air inlet, the rectifying still residue inlet is connected with a solid propeller, the rectifying still residue enters the oxygen-adjacent cracking device at a certain speed by the pushing of the solid propeller, the air inlet is connected with a fan, air is blown into the oxygen-adjacent cracking device by the fan, and the oxygen-adjacent cracking device is in a continuous rotation state; the outlet of the oxygen cracking device is connected with the inlet of the catalytic oxidation device through a pipeline, and the outlet of the catalytic oxidation device is connected with the exhaust gas discharge port.
The temporary oxygen cracking device is a horizontal temporary oxygen cracking reaction furnace.
The invention has the beneficial effects that:
the method is suitable for the kettle residue of which the boiling point or sublimation point of the oxide formed by any element in any rectifying kettle residue after the temporary oxygen cracking is not higher than 400 ℃. The rectifying still residue does not need to be pretreated, and the rectifying still residue can be treated at the temperature of not more than 550 ℃ by utilizing the bifunctional temporary oxygen cracking catalyst with cracking and oxidation, so that the defects of high fuel consumption and high treatment temperature in the traditional method are avoided, and the method has the characteristics of low treatment temperature and low cost; meanwhile, the invention also avoids the possibility of secondary pollution caused by VOC-containing flue gas generated by high-temperature incineration in the traditional method.
Drawings
FIG. 1 is a system for purifying and treating still residue in a distillation apparatus according to the present invention.
Detailed Description
The present invention will be described in further detail below with reference to specific embodiments and with reference to the attached drawings.
As shown in fig. 1, a purification treatment system for rectifying still residue comprises a horizontal near-oxygen cracking reaction furnace 1 and a catalytic oxidation device 2 which are connected in series in sequence, wherein the same end of the near-oxygen cracking reaction furnace 1 is respectively provided with a rectifying still residue inlet and an air inlet, the rectifying still residue inlet is connected with a solid propeller 3, the rectifying still residue enters the near-oxygen cracking reaction furnace at a certain speed by the pushing of the solid propeller, the air inlet is connected with a fan 4, air is blown into the near-oxygen cracking reaction furnace by the fan, and the rectifying still residue is fully contacted with a near-oxygen cracking catalyst when the near-oxygen cracking reaction furnace is in a continuous rotation state; the outlet of the temporary oxygen cracking reaction furnace 1 is connected with the inlet of the catalytic oxidation device 2 through a pipeline, and the outlet of the catalytic oxidation device is connected with a waste gas discharge port.
Based on above-mentioned system purification treatment rectifying still is incomplete, send rectifying still residue into in the face oxygen cracking reacting furnace under the promotion of solid propeller, in blowing air into face oxygen cracking reacting furnace through the fan, face oxygen cracking reacting furnace is in the state of continuous rotation, rectifying still residue is totally embedded by the flowing face oxygen cracking catalyst that rolls, use the air to carry out face oxygen cracking oxidation treatment as the oxidant, the gas that contains organic matter that cracking oxidation treatment produced gets into catalytic oxidation device and carries out catalytic oxidation treatment, realize deep purification elimination secondary pollution.
Example 1
The temporary oxygen cracking catalyst takes alumina as a carrier, calcium oxide (the load is 5%) and chromium oxide (the load is 5%) are loaded, and the particle size is 1-120 mu m. The catalytic oxidation catalyst is a honeycomb KND-691 noble metal catalyst (Shandong Kangnodel environmental protection equipment science and technology Co., Ltd.).
The rectifying still residue produced in the refining process of tert-butyl acrylate is detected to have an average molecular weight of 104563kg/kmol, and the rectifying still residue mainly consists of C, H, O.
In the critical oxygen cracking3 tons of temporary oxygen cracking catalyst are filled in the decomposition reaction furnace, the rectifying still residue is added into the reaction furnace at the speed of 3 tons/hour, and simultaneously, 45000m of air is introduced3The reaction temperature was maintained at 550 ℃ per hour. The detected concentration of organic impurities in the gas at the outlet of the oxygen cracking device is 4590mg/m3. Gas with a pressure of 10000h-1The space velocity of the gas passes through a catalytic oxidation device, the reaction temperature is maintained at 400 ℃, and the concentration of organic impurities in the gas at the outlet of the catalytic oxidation device is measured to be 14mg/m3。
Example 2
The near-oxygen cracking catalyst takes an HY molecular sieve as a carrier, and is loaded with beryllium oxide (the load is 5%) and copper oxide (the load is 25%) and has the particle size of 1-80 mu m. The catalytic oxidation catalyst is a honeycomb KND-691 noble metal catalyst.
The rectifying still residue produced in the refining process of the butyl acetate product is detected to have an average molecular weight of 15895kg/kmol, and the rectifying still residue mainly comprises C, H, O elements.
3 tons of temporary oxygen cracking catalyst are loaded into a temporary oxygen cracking reaction furnace, the distillation kettle residue is added into the reaction furnace at the speed of 3 tons/hour, and air 45000m is introduced at the same time3The reaction temperature was maintained at 500 ℃ per hour. The detected concentration of organic impurities in the gas at the outlet of the oxygen cracking device is 2460mg/m3. Gas with a pressure of 20000h-1The space velocity of the gas passes through the catalytic oxidation device, the reaction temperature is maintained at 250 ℃, and the concentration of the organic impurities in the gas at the outlet of the catalytic oxidation device is measured to be 48mg/m3。
Example 3
The temporary oxygen cracking catalyst takes mordenite as a carrier, and is loaded with calcium oxide (the load is 5%) and titanium oxide (the load is 25%), wherein the particle size is 20-200 mu m. The catalytic oxidation catalyst is a honeycomb KND-561 noble metal catalyst (Shandong Kangnodel environmental protection equipment science and technology Co., Ltd.).
The rectifying still residue generated in the process of producing benzaldehyde by the toluene chlorination hydrolysis method is detected to have an average molecular weight of 34223kg/kmol, and the rectifying still residue mainly comprises C, H, O, Cl elements.
3 tons of the catalyst for temporary oxygen cracking are loaded into a temporary oxygen cracking reaction furnace, and the distillation kettle residue is added at the rate of 1.5 tons/hourPutting the mixture into a reaction furnace, and simultaneously introducing air of 15000m3The reaction temperature was maintained at 450 ℃ per hour. The concentration of organic impurities in the gas at the outlet of the oxygen cracking device is 3855mg/m3. Gas with a pressure of 10000h-1The space velocity of the gas passes through the catalytic oxidation device, the reaction temperature is maintained at 380 ℃, and the concentration of the organic impurities in the gas at the outlet of the catalytic oxidation device is measured to be 44mg/m3。
Example 4
The temporary oxygen cracking catalyst takes mordenite as a carrier, barium oxide (the load is 2.5%) and cobalt oxide (the load is 15%) are loaded on the mordenite, and the carrier is zeolite with the particle size of 20-200 mu m. The catalytic oxidation catalyst is a honeycomb KND-691 noble metal catalyst.
The rectification still residue produced in the refining process of glyphosate products is detected to have an average molecular weight of 52134kg/kmol, and the rectification still residue mainly consists of C, H, O, P elements.
3 tons of temporary oxygen cracking catalyst are loaded into a temporary oxygen cracking reaction furnace, the distillation kettle residue is added into the reaction furnace at the speed of 3 tons/hour, and air 45000m is introduced at the same time3The reaction temperature was maintained at 500 ℃ per hour. The concentration of the organic impurities in the gas at the outlet of the oxygen cracking device is 1846mg/m3. Gas for 30000h-1The space velocity of the gas passes through the catalytic oxidation device, the reaction temperature is maintained at 450 ℃, and the concentration of the organic impurities in the gas at the outlet of the catalytic oxidation device is measured to be 42mg/m3。
Example 5
The temporary oxygen cracking catalyst takes HY molecular sieve as a carrier, and is loaded with magnesium oxide (the load is 2.5%) and vanadium oxide (the load is 12.5%), and the particle size is 1-80 μm. The catalytic oxidation catalyst is a honeycomb KND-561 noble metal catalyst.
The detection result shows that the average molecular weight of the rectifying still residue generated in the production process of nicosulfuron is 34242kg/kmol, and the rectifying still residue mainly comprises C, H, O, S elements.
3 tons of temporary oxygen cracking catalyst are loaded into a temporary oxygen cracking reaction furnace, the distillation kettle residue is added into the reaction furnace at the speed of 3 tons/hour, and air 45000m is introduced at the same time3The reaction temperature was maintained at 550 ℃ per hour. Detected in the gas at the outlet of the oxygen cracking deviceThe concentration of organic impurities is 1622mg/m3. Gas with a pressure of 20000h-1The space velocity of the gas passes through the catalytic oxidation device, the reaction temperature is maintained at 400 ℃, and the concentration of the organic impurities in the gas at the outlet of the catalytic oxidation device is measured to be 26mg/m3。
Example 6
The temporary oxygen cracking catalyst takes alumina as a carrier, calcium oxide (the load is 5%) and manganese oxide (the load is 15%) are loaded, and the particle size is 1-150 mu m. The catalytic oxidation catalyst is a honeycomb KND-691 noble metal catalyst.
The distillation still residue produced in the refining process of aniline product is detected to have an average molecular weight of 25034kg/kmol, and the distillation still residue mainly consists of C, H, O, N elements.
3 tons of oxygen cracking catalyst are loaded into the oxygen cracking reaction furnace, the distillation still residue is added into the reaction furnace at the speed of 1.5 tons/hour, and simultaneously air is introduced into the reaction furnace at the speed of 15000m3The reaction temperature was maintained at 450 ℃ per hour. The concentration of organic impurities in the gas at the outlet of the oxygen cracking device is 4212mg/m3. Gas with a pressure of 10000h-1The space velocity of the gas passes through the catalytic oxidation device, the reaction temperature is maintained at 450 ℃, and the concentration of the organic impurities in the gas at the outlet of the catalytic oxidation device is measured to be 31mg/m3。
Example 7
The temporary oxygen cracking catalyst takes alumina as a carrier, and is loaded with calcium oxide (the load is 5%) and cerium oxide (the load is 25%), and the particle size is 1-120 mu m. The catalytic oxidation catalyst is a honeycomb KND-691 noble metal catalyst.
The rectification still residue produced in the refining process of the tert-butyl acetate product is detected to have an average molecular weight of 12382kg/kmol, and the rectification still residue mainly comprises C, H, O elements.
3 tons of temporary oxygen cracking catalyst are loaded into a temporary oxygen cracking reaction furnace, the distillation kettle residue is added into the reaction furnace at the speed of 3 tons/hour, and air 45000m is introduced at the same time3The reaction temperature was maintained at 550 ℃ per hour. The concentration of organic impurities in the gas at the outlet of the oxygen cracking device is 1278mg/m3. Gas for 30000h-1The space velocity of the reaction is measured by a catalytic oxidation device through maintaining the reaction temperature at 325 DEG CThe concentration of organic impurities in the oral gas is 47mg/m3。
Claims (6)
1. A purification treatment method of distillation still residue is characterized by comprising the following steps: the horizontal type temporary oxygen cracking device is in a continuous rotating state, after the rectifying still residue enters the temporary oxygen cracking device, the temporary oxygen cracking oxidation treatment is carried out in the air atmosphere and in the presence of a temporary oxygen cracking catalyst, and the gas containing organic matters generated by the cracking oxidation treatment enters the catalytic oxidation device for catalytic oxidation treatment;
wherein the average molecular weight of the rectifying still residue is not less than 10000kg/kmol, and the boiling point or sublimation point of an oxide formed by any element in the rectifying still residue after the oxygen cracking is not higher than 400 ℃;
the distillation still residue accounts for 0.5-1 tonResidual kettle/(ton)Catalyst and process for preparing sameH) entering the temporary oxygen cracking device at a speed of ensuring that the rectification kettle residue is completely embedded by the rolling catalyst and simultaneously is 15000-25000 m3/(ton)Residual kettleH) air at a rate;
the temporary oxygen cracking catalyst is prepared by loading an oxide with alkalinity and an oxide with oxidability on a carrier; the supporting amount of the oxide with alkalinity is 1-5 wt%, and the supporting amount of the oxide with oxidability is 5-25 wt%; the oxide with alkalinity is one of calcium oxide, magnesium oxide, beryllium oxide or barium oxide, and the oxide with oxidability is one of copper oxide, chromium oxide, vanadium oxide, titanium oxide, cerium oxide, manganese oxide and cobalt oxide; the carrier is alumina, HY molecular sieve or mordenite;
the temperature of the oxygen cracking oxidation treatment is 450-550 ℃.
2. The purification treatment method of the rectifying still residue according to claim 1, wherein the particle size of the temporary oxygen cracking catalyst is 1 to 200 μm.
3. The method for purifying still residue according to claim 1, wherein the method comprisesThe content of organic matters in the outlet gas of the temporary oxygen cracking device is 500-5000 mg/m3。
4. The method for purifying and treating the distillation still residue according to claim 1, wherein the organic matter-containing gas is used for 10000 to 30000 hours-1The catalyst enters a catalytic oxidation device at a catalytic oxidation reaction temperature of 250-450 ℃.
5. The purification treatment method of the rectifying still residue according to claim 1, wherein the catalyst used in the catalytic oxidation treatment is a mechanically molded catalyst of a temporary oxygen cracking catalyst or a catalytic combustion catalyst.
6. The purification treatment method of the rectifying still residue according to claim 1 or 4, wherein the content of organic matters in the outlet gas of the catalytic oxidation device is 0-50 mg/m3。
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