CN107261844B - Production process of vehicle urea containing nano-scale catalyst - Google Patents
Production process of vehicle urea containing nano-scale catalyst Download PDFInfo
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- CN107261844B CN107261844B CN201710671759.6A CN201710671759A CN107261844B CN 107261844 B CN107261844 B CN 107261844B CN 201710671759 A CN201710671759 A CN 201710671759A CN 107261844 B CN107261844 B CN 107261844B
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- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 239000004202 carbamide Substances 0.000 title claims abstract description 35
- 239000003054 catalyst Substances 0.000 title claims abstract description 32
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000000746 purification Methods 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 11
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 10
- 230000008569 process Effects 0.000 claims abstract description 8
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 230000008020 evaporation Effects 0.000 claims description 3
- 238000005374 membrane filtration Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 230000000087 stabilizing effect Effects 0.000 claims description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 abstract description 15
- 238000002425 crystallisation Methods 0.000 abstract description 5
- 230000008025 crystallization Effects 0.000 abstract description 5
- 230000000593 degrading effect Effects 0.000 abstract description 5
- 238000003912 environmental pollution Methods 0.000 abstract description 4
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 12
- 230000000694 effects Effects 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 229910052815 sulfur oxide Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- 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
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9404—Removing only nitrogen compounds
- B01D53/9409—Nitrogen oxides
- B01D53/9413—Processes characterised by a specific catalyst
- B01D53/9418—Processes characterised by a specific catalyst for removing nitrogen oxides by selective catalytic reduction [SCR] using a reducing agent in a lean exhaust gas
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
- B01D2251/2067—Urea
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/01—Engine exhaust gases
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Biomedical Technology (AREA)
- Environmental & Geological Engineering (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
The invention discloses a production process of vehicle urea containing a nano-scale catalyst, which has the advantages that by adding a catalyst A, optimizing a continuous purification process and a process for reducing the ammonia content, the problem of heavy metal environmental pollution of the vehicle urea can be effectively reduced, the efficiency of degrading and absorbing nitric oxide of the vehicle urea is improved, and the problem of low-temperature crystallization is solved. The catalyst A added in the process has the characteristics of high catalytic activity, wide temperature window, quick ignition and the like.
Description
Technical Field
The invention relates to a production process of automobile urea containing a nano-scale catalyst, belonging to the technical field of chemical industry.
Background
The urea-scr (selective Catalytic reduction) technology has been widely used in developed countries and regions such as europe as an important means for controlling exhaust emissions of automotive diesel engines due to its advantages of improved fuel consumption, high sulfur poisoning resistance, and the like, and plays an important role in improving air pollution caused by automobile exhaust. At present, although several domestic main automotive diesel engine enterprises have developed research on the SCR technology in the field of diesel engines, the research is mainly based on foreign technology introduction and application, and the core technology is still mainly mastered by foreign related manufacturers, which becomes the main bottleneck of popularization and application of the technology in China.
The diesel engine for the vehicle has the advantages of variable operation conditions, wide exhaust flow and temperature change range, different contents of components such as nitrogen oxides, sulfur oxides, smoke dust and the like in exhaust gas, different reaction conditions of the catalyst, different proportions of effective components in the catalyst, different selection of auxiliary components, different preparation process and different performance evaluation conditions, and the like, and the change of the proportions and the preparation method usually changes the interaction between the carrier and the active component, thereby finally influencing the activity of the catalyst.
Thirdly, the additives of the automobile urea product are toxic, so that after being used by customers, the additive has great harm to the environment and has certain threat to the health and the safety of the customers. Therefore, the research and development of the non-toxic, high-efficiency and low-temperature-resistant automobile urea can effectively solve the problem of heavy metal environmental pollution of the automobile urea, provide the efficiency of the automobile urea for degrading nitric oxide, solve the problem of low-temperature crystallization, ensure the good operation of SCR systems of national and four commercial vehicles, ensure the normal starting of the vehicles and the normal operation of the SCR systems in low-temperature weather, reduce the emission of NOx at low temperature, have the ammonia release potential value of more than 200g/kg, completely match the existing SCR design, solve the problem of ammonia release potential value matching, effectively prevent the damage of a urea delivery pipe and a storage tank caused by low-temperature volume expansion, and reduce the use cost of the whole automobile.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention provides a production process of vehicle urea containing a nano-scale catalyst, the vehicle urea produced by the process can effectively reduce the heavy metal environmental pollution problem of the vehicle urea, improve the efficiency of degrading and absorbing nitrogen oxides of the vehicle urea, and solve the problem of low-temperature crystallization.
The invention discloses a production process of automobile urea containing a nano-scale catalyst, which comprises the following steps:
a. preparing a catalyst A, dissolving 50-80g of ammonium metavanadate and oxalic acid with equal mass in 1000g of deionized water to prepare a solution, adding 30-40g of sodium metaaluminate, stirring, adding 20g of nano WO3/TiO2 mixture powder in the stirring process, continuously stirring for 2 hours, placing the mixture into a temperature-controlled electric furnace, roasting at the high temperature of 450 ℃ for 1 hour, and naturally cooling to the room temperature to obtain the catalyst A.
b. And (3) stabilizing the catalyst A: and putting the prepared catalyst A into the electric furnace again, heating to 650-680 ℃ in a steam atmosphere, heating for 30 minutes, and naturally cooling to room temperature.
c. Preparing a urea solution: at the temperature of 20-25 ℃, mixing urea and deionized water according to the weight ratio of 1:2, purifying for four times to ensure that insoluble substances are lower than 2%, and adding the deionized water again to ensure that the concentration of the urea solution reaches 32%.
d. And (3) reducing the content of free ammonia: and c, passing the solution prepared in the step c through a rectifying tower and a flash evaporation tank to enable the content of free ammonia to be lower than 0.2%.
e. Adding the catalyst A into the urea solution, stirring for 30min at normal temperature, and storing for later use.
Preferably, the resistivity of the deionized water is below 15M Ω cm.
Preferably, the four purifications are bag filter purification, mechanical filter purification, precise filter element purification and membrane filtration purification respectively.
The method has the advantages that by adding the catalyst A, optimizing the continuous purification process and the ammonia content reduction process, the problem of heavy metal environmental pollution of the automobile urea can be effectively reduced, the efficiency of degrading and absorbing nitric oxide by the automobile urea is improved, and the problem of low-temperature crystallization is solved. The catalyst A added in the process has the characteristics of high catalytic activity, wide temperature window, quick ignition and the like.
Detailed Description
In order to more clearly understand the technical solution of the present invention.
The indexes of the urea aqueous solution for vehicles meet the ISO2241-1 regulation, the detection method is implemented by adopting the method of ISO2241-2, the specific indexes are shown in the table 1, and the DeNOx effect is tested by adopting an activity evaluation test device of a standard SCR, and the NOx conversion rate is used as an index.
TABLE 1
Example 1, a. preparing catalyst A, dissolving 50-80g ammonium metavanadate and oxalic acid with equal mass into 1000g deionized water to prepare solution, adding 30-40g sodium metaaluminate and stirring, adding 20g nano-scale WO3/TiO2 mixture powder in the stirring process, continuously stirring for 2 hours, placing into a temperature-controlled electric furnace, roasting at 450 ℃ for 1 hour, and naturally cooling to room temperature to obtain catalyst A.
b. And (3) stabilizing the catalyst A: and putting the prepared catalyst A into the electric furnace again, heating to 650-680 ℃ in a steam atmosphere, heating for 30 minutes, and naturally cooling to room temperature.
c. Preparing a urea solution: at the temperature of 20-25 ℃, mixing urea and deionized water according to the weight ratio of 1:2, purifying for four times to ensure that insoluble substances are lower than 2%, and adding the deionized water again to ensure that the concentration of the urea solution reaches 32%.
d. And (3) reducing the content of free ammonia: and c, passing the solution prepared in the step c through a rectifying tower and a flash evaporation tank to enable the content of free ammonia to be lower than 0.2%.
e. Adding the catalyst A into the urea solution, stirring for 30min at normal temperature, and storing for later use.
Preferably, the resistivity of the deionized water is below 15M Ω cm.
Preferably, the four purifications are bag filter purification, mechanical filter purification, precise filter element purification and membrane filtration purification respectively.
As shown in Table 2, the solution after four-stage purification and addition of the catalyst A completely meets the requirements of ISO22241-1, the capability of degrading nitrogen oxides is improved, and the crystallization temperature is far lower than the national standard.
The above description is only a preferred embodiment of the present invention, and all equivalent changes or modifications of the structure, characteristics and principles described in the present invention are included in the scope of the present invention.
Claims (3)
1. A production process of automobile urea containing a nano-scale catalyst comprises the following steps:
a. preparing a catalyst A: 50-80g of ammonium metavanadate and oxalic acid with equal mass are dissolved in 1000g of deionized water to prepare a solution, 30-40g of sodium metaaluminate is added and stirred, and 20g of nano WO is added in the stirring process3/TiO2Continuously stirring the mixture powder for 2 hours, putting the mixture powder into a temperature-controlled electric furnace, roasting the mixture powder for 1 hour at the high temperature of 450 ℃, and naturally cooling the mixture powder to the room temperature to obtain a catalyst A;
b. and (3) stabilizing the catalyst A: putting the prepared catalyst A into an electric furnace again, heating to the high temperature of 650-680 ℃ in a steam atmosphere, heating for 30 minutes, and naturally cooling to room temperature;
c. preparing a urea solution: at 20-25 ℃, mixing urea and deionized water according to the weight ratio of 1:2 parts by weight of the urea solution are mixed, the mixture is purified for four times to ensure that the content of insoluble substances is less than 2 percent, and the deionized water is added again to ensure that the concentration of the urea solution reaches 32 percent;
d. and (3) reducing the content of free ammonia: c, enabling the solution prepared in the step c to pass through a rectifying tower and a flash evaporation tank to enable the content of free ammonia to be lower than 0.2%;
e. adding the catalyst A into the urea solution, stirring for 30min at normal temperature, and storing for later use.
2. The process for producing automotive urea containing nano-scale catalyst according to claim 1, wherein: the deionized water has a resistivity of less than 15M Ω cm.
3. The process for producing automotive urea containing nano-scale catalyst according to claim 1, wherein: the four purifications are respectively bag filter purification, mechanical filter purification, precise filter element purification and membrane filtration purification.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710671759.6A CN107261844B (en) | 2017-08-08 | 2017-08-08 | Production process of vehicle urea containing nano-scale catalyst |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710671759.6A CN107261844B (en) | 2017-08-08 | 2017-08-08 | Production process of vehicle urea containing nano-scale catalyst |
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| CN107261844A CN107261844A (en) | 2017-10-20 |
| CN107261844B true CN107261844B (en) | 2020-06-02 |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108499360A (en) * | 2018-04-14 | 2018-09-07 | 长沙小新新能源科技有限公司 | A kind of urea for vehicle and preparation method thereof containing catalyst |
| CN110339866A (en) * | 2019-07-14 | 2019-10-18 | 茌平县鲁华工贸有限公司 | A kind of urea for vehicle production catalyst and its production technology |
| CN112110835A (en) * | 2020-09-30 | 2020-12-22 | 河南弘康环保科技有限公司 | Automobile urea capable of preventing urea biuret, cyanuric acid and melamine intermediate products from being generated and preparation method thereof |
| CN112090277A (en) * | 2020-09-30 | 2020-12-18 | 河南弘康环保科技有限公司 | Production process of vehicle urea containing nano-scale catalyst |
| CN112316723A (en) * | 2020-11-13 | 2021-02-05 | 河南弘康环保科技有限公司 | Automobile urea solution for efficiently solving crystallization blockage |
| CN112316722A (en) * | 2020-11-13 | 2021-02-05 | 河南弘康环保科技有限公司 | Preparation method of antifreezing quality-guaranteeing type automobile urea solution added with multiple active agents |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE20219608U1 (en) * | 2002-12-05 | 2003-06-12 | Erhard & Soehne Gmbh | Tank for car used liquids, such as urea or its solutions and/or fuel used particularly in catalyzer fitted behind car IC engine |
| CN101711978A (en) * | 2009-11-28 | 2010-05-26 | 江苏中科节能环保技术有限公司 | High mechanical property and low cost SCR denitration catalyst and preparation method thereof |
| DE102010020842A1 (en) * | 2010-05-18 | 2011-11-24 | Continental Automotive Gmbh | Filling level sensor for detecting e.g. filling level height of urea solution in reducing agent container, for selective catalytic reduction system of motor car, has electrodes connected via resistor to detect height and conductance |
| CN102806011A (en) * | 2011-06-03 | 2012-12-05 | 中国石油化工股份有限公司 | Method for preparing automobile urea liquid reducing agent |
| GB201322576D0 (en) * | 2013-12-19 | 2014-02-05 | Equigerminal Sa | Urea delivery system for scr system |
-
2017
- 2017-08-08 CN CN201710671759.6A patent/CN107261844B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| DE20219608U1 (en) * | 2002-12-05 | 2003-06-12 | Erhard & Soehne Gmbh | Tank for car used liquids, such as urea or its solutions and/or fuel used particularly in catalyzer fitted behind car IC engine |
| CN101711978A (en) * | 2009-11-28 | 2010-05-26 | 江苏中科节能环保技术有限公司 | High mechanical property and low cost SCR denitration catalyst and preparation method thereof |
| DE102010020842A1 (en) * | 2010-05-18 | 2011-11-24 | Continental Automotive Gmbh | Filling level sensor for detecting e.g. filling level height of urea solution in reducing agent container, for selective catalytic reduction system of motor car, has electrodes connected via resistor to detect height and conductance |
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