CN104557616B - A kind of method of urea synthesis solution - Google Patents
A kind of method of urea synthesis solution Download PDFInfo
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- CN104557616B CN104557616B CN201410805818.0A CN201410805818A CN104557616B CN 104557616 B CN104557616 B CN 104557616B CN 201410805818 A CN201410805818 A CN 201410805818A CN 104557616 B CN104557616 B CN 104557616B
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- carbon dioxide
- ammonia
- high pressure
- water
- pressure
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- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 239000004202 carbamide Substances 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 27
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 19
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 19
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 136
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 103
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 82
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 67
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 50
- 239000007788 liquid Substances 0.000 claims abstract description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 9
- 230000006835 compression Effects 0.000 claims abstract description 8
- 238000007906 compression Methods 0.000 claims abstract description 8
- 238000009833 condensation Methods 0.000 claims abstract description 8
- 230000005494 condensation Effects 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 36
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 8
- 239000003921 oil Substances 0.000 claims description 7
- 229910000069 nitrogen hydride Inorganic materials 0.000 claims description 6
- 238000006477 desulfuration reaction Methods 0.000 claims description 4
- 230000023556 desulfurization Effects 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- 238000005259 measurement Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229910052756 noble gas Inorganic materials 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000005516 engineering process Methods 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000000746 purification Methods 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 238000000354 decomposition reaction Methods 0.000 abstract description 3
- 238000004880 explosion Methods 0.000 abstract description 3
- 230000003247 decreasing effect Effects 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 238000009434 installation Methods 0.000 abstract description 2
- 235000013877 carbamide Nutrition 0.000 description 19
- 239000007789 gas Substances 0.000 description 7
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- PPBAJDRXASKAGH-UHFFFAOYSA-N azane;urea Chemical compound N.NC(N)=O PPBAJDRXASKAGH-UHFFFAOYSA-N 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 206010012735 Diarrhoea Diseases 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Treating Waste Gases (AREA)
Abstract
A kind of method that the invention discloses urea synthesis solution, concrete steps include: 1, the compression of carbon dioxide and purification；2, the purification of ammonia and conveying；3, the synthesis of urea liquid。This production technology due to ammonia from stripping effect, make first ammonium resolution ratio increase, thus in decreasing, low pressure decomposition reclaim load, power consumption reduces therewith, the first ammonium separated under High Temperature High Pressure, heat during its condensation is effectively utilized, and total energy consumption reduces, additionally operating flexibility is big, running rate is high, and explosion hazard is little, and installation and repairing is convenient, process condensate can utilize by secondary, pollution-free；In urea liquid building-up process, the conversion ratio of carbon dioxide and ammonia is high, and remains unreacted carbon dioxide and ammonia can circulate and make full use of, and raw material availability, close to 100%, greatly reduces cost。
Description
Technical field
A kind of method that the present invention relates to urea synthesis solution, belongs to chemical field。
Background technology
Carbamide is the chemical products on a kind of basis, and China is large agricultural country, and amount of urea is huge, and the relationship between productivity of carbamide is to National agricultural food safety。The production technology that current big-and-middle-sized urea plant adopts has: water solution total cycling method, middle pressure integrated ammonia urea process, carbon dioxide stripping process, ammonia stripping process。
Water solution total cycling method: the most of middle-size and small-size urea plant of this Fa Shi China produces the method adopted, mature production technology, convenient and reliable operation, pump and non-standard equipment all domesticize, being characterized in synthetic tower, conversion ratio is higher, and unreacted reactant adopts two-stage nitration decompression to decompose, and power consumption is bigger, tail gas pressure, temperature are all relatively low, and the danger of blast is little。
Carbon dioxide stripping process: from the seventies, China successively introduces tens set carbon dioxide stripping process urea plants, it mostly is large-scale plant, being characterized in that technological process is short, synthesis pressure is low, and power consumption is few, but operating condition is harsh, corrosion is comparatively serious, and tail gas fires danger, and operating flexibility is little。Modified model CO2Vaporizing extract process, unstripped gas is additionally arranged desulfurization dehydrogenation unit, alleviates corrosion, reduces explosion danger, and meanwhile, one-time investment is also bigger。
Middle pressure integrated ammonia urea process: the synthesis ammonia plant that it is raw material with natural gas that this method is applicable to, is characterized in that diarrhea of heat type is made good use of, and resolution ratio is high, eliminates low pressure decomposition, simplifies flow process, owing to first ammonium temperature is higher, and HO2/CO2Relatively low。The corrosion of first ammonium pump is more serious, and the material requirements of pump is harsh。
All there is distinct disadvantage and limitation in visible above-mentioned main flow urea production process。
Summary of the invention
For prior art Problems existing, the present invention provides a kind of method of urea synthesis solution, and concrete steps include:
(1), the carbon dioxide come from carbon dioxide storage tank conveying first passes through a carbon dioxide drop separator with water seal, water in carbon dioxide is removed, subsequently into five sections of compressors of carbon dioxide, carbon dioxide is after one, two, three sections are compressed, pressure is about 2.4MPa, temperature is 40 DEG C, after entering oil removing desulfurizer desulfurization, entrance is pressed CO2 heater steam heat, temperature rises to more than 150 DEG C, enter dehydrogenation reactor, the H in carbon dioxide in dehydrogenation reactor2It is burned off with other imflammable gas, then carbon dioxide presses carbon dioxide cooler in entering, and but enters gas-liquid separator afterwards by cooling water-cooled, and the carbon dioxide after separation is back to four sections of entrances of carbon-dioxide gas compressor, then through four, five sections of compressions, final absolute pressure 14.6MPa；
(2), raw materials ammonia is sent here from synthesis ammonia storehouse, ammonia workshop, enter liquid ammonia filter and remove entrained solid impurity and oils in liquefied ammonia, subsequently into liquefied ammonia dashpot, high-pressure ammonia pump is entered after flow measurement, sending into high-pressure injector after liquefied ammonia being pressurized to absolute pressure 18.34MPa with high-pressure ammonia pump, high-pressure injector connects high pressure condenser；
(3), high pressure condenser top is sent into through the carbon dioxide of five sections of compressions, also the top of high pressure condenser is delivered to from the liquefied ammonia that high-pressure injector is next, above two logistics mixes mutually in high pressure condenser, controls to enter flow and makes the NH of entrance high pressure condenser3/CO2Mol ratio is 3～3.5, high pressure condenser is provided with vertical tube, the temperature at high pressure condenser top is about 180～183 DEG C, urea synthesis tower bottom is flowed into by overflow pipe by the first ammonium liquid come bottom high pressure condenser, ammonia and carbon dioxide mixture, synthetic tower liquid level is maintained at above overflow pipe funnel at least 1 meter, being provided with 11 pieces of sieve plates in synthetic tower, urea liquid flows out bottom urea synthesizer；
(4), containing unconverted NH3And CO2And noble gas sent into high pressure scrubber by synthetic tower, in high pressure scrubber, NH3And CO2Condensed fully, it is provided with cooler in high pressure scrubber bottom, cooler adopts tempered water to cool down, with high pressure scrubber water circulating pump, tempered water is successively flow through high pressure scrubber and high pressure scrubber water recirculator, tempered water removes the condensation heat in high pressure scrubber, so that the temperature of tempered water is heated to 95 DEG C by 80 DEG C, this heat is removed by high pressure scrubber water recirculator, tempered water is cooled to 80 DEG C from 95 DEG C again, in this closed-cycle system, temperature is to automatically control with controlling to flow through the flow of high pressure scrubber water recirculator, the liquefied ammonia that condensation obtains returns to ammonia storehouse, carbon dioxide returns carbon dioxide storage tank。
Step (1) enters CO in the carbon dioxide of carbon dioxide drop separator2Volumetric concentration is more than 96%, and pressure is 0.005MPa, temperature≤40 DEG C。
Five sections of compressors of carbon dioxide are four row five cylinder opposed balance compressors。
The temperature of raw materials ammonia is about 30 DEG C, and absolute pressure is about 2.5MPa。
It is an advantage of the current invention that:
(1) this production technology due to ammonia from stripping effect, make first ammonium resolution ratio increase, thus in decreasing, low pressure decomposition reclaim load, power consumption reduces therewith, the first ammonium separated under High Temperature High Pressure, heat during its condensation is effectively utilized, and total energy consumption reduces, additionally operating flexibility is big, running rate is high, and explosion hazard is little, and installation and repairing is convenient, process condensate can utilize by secondary, pollution-free；
(2) in urea liquid building-up process, the conversion ratio of carbon dioxide and ammonia is high, and remains unreacted carbon dioxide and ammonia can circulate and make full use of, and raw material availability, close to 100%, greatly reduces cost。
Accompanying drawing explanation
Fig. 1 is compression and the purification process schematic diagram of carbon dioxide。
Fig. 2 is purification and the conveying schematic flow sheet of ammonia。
Fig. 3 is urea liquid synthesis flow schematic diagram。
1-carbon dioxide storage tank, 2-carbon dioxide drop separator, five sections of compressors of 3-carbon dioxide, one to five section of compressor of 31 to 35-, 4-oil removing desulfurizer, 5-presses CO2 heater, 6-dehydrogenation reactor, 7-presses carbon dioxide cooler, 8-gas-liquid separator, 9-high pressure condenser, 10-liquid ammonia filter, 11-liquefied ammonia dashpot, 12-high-pressure ammonia pump, 13-high-pressure injector, 14-urea synthesizer, 15-overflow pipe, 16-high pressure scrubber, 17-high pressure scrubber water recirculator。
Detailed description of the invention
In conjunction with Figure of description 1-3, the method for the urea synthesis solution of the present invention is specifically introduced:
(1), first pass through a carbon dioxide drop separator 2 with water seal from the carbon dioxide that carbon dioxide storage tank 1 conveying is next, the water in carbon dioxide is removed, enters CO in the carbon dioxide of carbon dioxide drop separator 22Volumetric concentration is more than 96%, and pressure is 0.005MPa, temperature≤40 DEG C。Subsequently into five sections of compressors 3 of carbon dioxide, five sections of compressors of carbon dioxide are four row five cylinder opposed balance compressors, carbon dioxide is after one, two, three sections are compressed, pressure is about 2.4MPa, and temperature is 40 DEG C, after entering oil removing desulfurizer 4 desulfurization, entrance is pressed CO2 heater 5 heat with steam, temperature rises to more than 150 DEG C, enters dehydrogenation reactor 6, the H in carbon dioxide in dehydrogenation reactor 62It is burned off with other imflammable gas, then carbon dioxide presses carbon dioxide cooler 7 in entering, but gas-liquid separator 8 is entered afterwards by cooling water-cooled, carbon dioxide after separation is back to four section of 34 entrance of carbon-dioxide gas compressor, then through four, five sections of compressions, final absolute pressure 14.6MPa；
(2), temperature is about 30 DEG C, absolute pressure is about the raw materials ammonia of 2.5MPa and sends here from synthesis ammonia storehouse, ammonia workshop, enter liquid ammonia filter 10 and remove entrained solid impurity and oils in liquefied ammonia, subsequently into liquefied ammonia dashpot 11, high-pressure ammonia pump 12 is entered after flow measurement, sending into high-pressure injector 13 after being pressurized to absolute pressure 18.34MPa with 12 liquefied ammonia of high-pressure ammonia pump, high-pressure injector 13 connects high pressure condenser 9；
(3), high pressure condenser 9 top is sent into through the carbon dioxide of five sections of compressions, also the top of high pressure condenser 9 is delivered to from the liquefied ammonia that high-pressure injector is next, above two logistics mixes mutually in high pressure condenser, controls to enter flow and makes the NH of entrance high pressure condenser3/CO2Mol ratio is 3～3.5, high pressure condenser 9 is provided with vertical tube, the temperature at high pressure condenser 9 top is about 180～183 DEG C, flowed into bottom urea synthesizer 14 by the first ammonium liquid come bottom high pressure condenser 9, ammonia and carbon dioxide mixture by overflow pipe, synthetic tower liquid level is maintained at above overflow pipe 15 funnel at least 1 meter, being provided with 11 pieces of sieve plates in synthetic tower, urea liquid flows out bottom urea synthesizer 14；
(4), containing unconverted NH3And CO2And noble gas is by synthetic tower feeding high pressure scrubber 16, in high pressure scrubber, NH3And CO2Condensed fully, it is provided with cooler 17 in high pressure scrubber bottom, cooler adopts tempered water to cool down, with high pressure scrubber water circulating pump, tempered water is successively flow through high pressure scrubber 16 and high pressure scrubber water recirculator 17, tempered water removes the condensation heat in high pressure scrubber, so that the temperature of tempered water is heated to 95 DEG C by 80 DEG C, this heat is removed by high pressure scrubber water recirculator, tempered water is cooled to 80 DEG C from 95 DEG C again, in this closed-cycle system, temperature is to automatically control with controlling to flow through the flow of high pressure scrubber water recirculator, the liquefied ammonia that condensation obtains returns to ammonia storehouse, carbon dioxide returns carbon dioxide storage tank 1。
Claims (4)
1. the method for a urea synthesis solution, it is characterised in that concrete steps include:
(1), the carbon dioxide come from carbon dioxide storage tank conveying first passes through a carbon dioxide drop separator with water seal, water in carbon dioxide is removed, subsequently into five sections of compressors of carbon dioxide, carbon dioxide is after one, two, three sections are compressed, pressure is 2.4MPa, temperature is 40 DEG C, after entering oil removing desulfurizer desulfurization, entrance is pressed CO2 heater steam heat, temperature rises to more than 150 DEG C, enter dehydrogenation reactor, the H in carbon dioxide in dehydrogenation reactor2It is burned off with other imflammable gas, then carbon dioxide presses carbon dioxide cooler in entering, and but enters gas-liquid separator afterwards by cooling water-cooled, and the carbon dioxide after separation is back to four sections of entrances of carbon-dioxide gas compressor, then through four, five sections of compressions, final absolute pressure 14.6MPa；
(2), raw materials ammonia is sent here from synthesis ammonia storehouse, ammonia workshop, enter liquid ammonia filter and remove entrained solid impurity and oils in liquefied ammonia, subsequently into liquefied ammonia dashpot, high-pressure ammonia pump is entered after flow measurement, sending into high-pressure injector after liquefied ammonia being pressurized to absolute pressure 18.34MPa with high-pressure ammonia pump, high-pressure injector connects high pressure condenser；
(3), high pressure condenser top is sent into through the carbon dioxide of five sections of compressions, also the top of high pressure condenser is delivered to from the liquefied ammonia that high-pressure injector is next, above two logistics mixes mutually in high pressure condenser, controls to enter flow and makes the NH of entrance high pressure condenser3/CO2Mol ratio is 3～3.5, high pressure condenser is provided with vertical tube, the temperature at high pressure condenser top is 180～183 DEG C, urea synthesis tower bottom is flowed into by overflow pipe by the first ammonium liquid come bottom high pressure condenser, ammonia and carbon dioxide mixture, synthetic tower liquid level is maintained at above overflow pipe funnel at least 1 meter, being provided with 11 pieces of sieve plates in synthetic tower, urea liquid flows out bottom urea synthesizer；
(4), containing unconverted NH3And CO2And noble gas sent into high pressure scrubber by synthetic tower, in high pressure scrubber, NH3And CO2Condensed fully, it is provided with cooler in high pressure scrubber bottom, cooler adopts tempered water to cool down, with high pressure scrubber water circulating pump, tempered water is successively flow through high pressure scrubber and high pressure scrubber water recirculator, tempered water removes the condensation heat in high pressure scrubber, so that the temperature of tempered water is heated to 95 DEG C by 80 DEG C, this heat is removed by high pressure scrubber water recirculator, tempered water is cooled to 80 DEG C from 95 DEG C again, in this closed-cycle system, temperature is to automatically control with controlling to flow through the flow of high pressure scrubber water recirculator, the liquefied ammonia that condensation obtains returns to ammonia storehouse, carbon dioxide returns carbon dioxide storage tank。
2. the method for urea synthesis solution according to claim 1, it is characterised in that enter CO in the carbon dioxide of carbon dioxide drop separator in step (1)2Volumetric concentration is more than 96%, and pressure is 0.005MPa, temperature≤40 DEG C。
3. the method for urea synthesis solution according to claim 1, it is characterised in that five sections of compressors of carbon dioxide are four row five cylinder opposed balance compressors。
4. the method for urea synthesis solution according to claim 1, it is characterised in that the temperature of raw materials ammonia is 30 DEG C, absolute pressure 2.5MPa。
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| CN201410805818.0A CN104557616B (en) | 2014-12-22 | 2014-12-22 | A kind of method of urea synthesis solution |
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| CN109516931A (en) * | 2018-12-12 | 2019-03-26 | 河南心连心化肥有限公司 | The device and production technology of a kind of low biuret urea for vehicle solution of continuous production |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0504966A1 (en) * | 1991-03-22 | 1992-09-23 | SNAMPROGETTI S.p.A. | Urea production process of high energy efficiency |
| CN1074901A (en) * | 1992-12-23 | 1993-08-04 | 中国五环化学工程公司 | Producing urea with increased yield by stripping with CO 2 novel process and device |
| CN1086511A (en) * | 1993-08-02 | 1994-05-11 | 中国五环化学工程总公司 | Energy-conservation, joint money, safety type urea production process and device |
| US5849952A (en) * | 1989-09-15 | 1998-12-15 | Shamprogetti S.P.A. | Urea production process with high energy efficiency |
| CN1554643A (en) * | 2003-12-25 | 2004-12-15 | 黑龙江黑化集团有限公司 | Method and apparatus for improving industrial producing urea |
-
2014
- 2014-12-22 CN CN201410805818.0A patent/CN104557616B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5849952A (en) * | 1989-09-15 | 1998-12-15 | Shamprogetti S.P.A. | Urea production process with high energy efficiency |
| EP0504966A1 (en) * | 1991-03-22 | 1992-09-23 | SNAMPROGETTI S.p.A. | Urea production process of high energy efficiency |
| CN1074901A (en) * | 1992-12-23 | 1993-08-04 | 中国五环化学工程公司 | Producing urea with increased yield by stripping with CO 2 novel process and device |
| CN1086511A (en) * | 1993-08-02 | 1994-05-11 | 中国五环化学工程总公司 | Energy-conservation, joint money, safety type urea production process and device |
| CN1554643A (en) * | 2003-12-25 | 2004-12-15 | 黑龙江黑化集团有限公司 | Method and apparatus for improving industrial producing urea |
Non-Patent Citations (1)
| Title |
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| 浅谈尿素的工艺流程及设计特点;孙盛杰和杨树禹;《黑龙江科技信息》;20121231(第4期);23页 * |
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