CN102910583A - Sulfur-tolerance shift reactor and sulfur-tolerance shift process for high-concentration CO - Google Patents
Sulfur-tolerance shift reactor and sulfur-tolerance shift process for high-concentration CO Download PDFInfo
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- CN102910583A CN102910583A CN2012102906505A CN201210290650A CN102910583A CN 102910583 A CN102910583 A CN 102910583A CN 2012102906505 A CN2012102906505 A CN 2012102906505A CN 201210290650 A CN201210290650 A CN 201210290650A CN 102910583 A CN102910583 A CN 102910583A
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Abstract
The invention relates to a sulfur-tolerance shift reactor and a sulfur-tolerance shift process for high-concentration CO, which belong to the technical field of sulfur-tolerance shift. The reactor comprises a reactor shell, wherein a gas inlet pipe is arranged at the upper part of the reactor shell and a gas outlet pipe is arranged at the lower part of the reactor shell; an upper catalyst bed layer and a lower catalyst bed layer are arranged in the reactor shell; and a water inlet pipe is arranged on the shell between the two catalyst bed layers. Process gas enters into the reactor from the gas inlet pipe, is subjected to shift reaction through the upper catalyst bed layer, is mixed with water entering from the water inlet pipe and finally enters into the lower catalyst bed layer to be subjected to shift reaction. According to the reactor, the water-gas ratio of the process gas from a gasification unit is not changed, the steam consumption is low, and a pre-reactor and a heat exchanger are not needed, so that the danger of methanation reaction is avoided, the ultrahigh temperature of the bed layers of the shift reactor can be effectively prevented, and heat generated by the shift reaction in the reactor can be fully utilized.
Description
Technical field
The present invention relates to a kind of sulfur-tolerant water gas shift device and sulfur resistant conversion process for high concentration CO, belong to the sulfur-resisting transformation technical field.
Background technology
In the technique coal gas that gasification produces, take Shell, GSP, east stove, space flight stove etc. as the process gas that fine coal gasification process was produced of representative in the butt of CO form and to be roughly 60%～75%.CO is up to entering shift-converter more than 60%, under the same transformationreation condition, the temperature of reaction of reaction bed bottom generally can be near 500 ℃, even above 530 ℃, so just special requirement has been proposed the material of reactor, increase the cost of reactor, also increased the insecurity of device operation.
The method of solution high concentration CO conversion overtemperature is a kind of at present is to adopt high water-gas ratio to reduce bed temperature, can be down to the temperature of bed bottom below 460 ℃ as water-gas ratio being brought up to about 1.8; The steam that the steam that adds can adopt the exothermic heat of reaction of utilization own to produce, but need to use waste heat boiler, invest larger; Another kind is to increase a pre-reactor before main transformer changes reactor, and pre-shift reaction product enters main transformer again and changes reactor after spray cooling or heat exchange cooling, also need additionally to increase equipment; Also having a kind of method is that the first shift-converter adopts very low water-gas ratio (such as 0.2～0.4), limits the transformation efficiency of CO, but along with reaction to carry out water-gas ratio more and more lower, under high temperature, low water-gas ratio, have the danger that methanation reaction occurs; And coal gasification adopts chilling process basically at present, and water-gas ratio is 0.8 ~ 1.2, if the employing water-gas ratio is 0.2 ~ 0.4 low water-gas ratio conversion process, needs lower water-gas ratio first, enters subsequent conversion and adds water or steam before again.
Can it seems thus, for the transformation system of high-concentration carbon monoxide, the increase of shift-converter load and the overheated overtemperatute of transformation catalyst that causes are the normal keys of producing of the present gasifying powder coal device of puzzlement always in the prior art.
Summary of the invention
Technical problem to be solved by this invention provides a kind of the change from high concentration CO sulfur-tolerant water gas shift device and the sulfur resistant conversion process of the next process gas water-gas ratio of gasification unit, its steam consumption is low, and pre-reactor and interchanger need not be set, avoid occuring the danger of methanation reaction, not only can prevent effectively that the shift-converter bed temperature is too high, and the heat that reactor inner conversion reaction is produced is fully used.
Sulfur-tolerant water gas shift device for high concentration CO of the present invention, comprise reactor shell, reactor shell top arranges admission line, the bottom sets out gas pipeline, reactor shell inside arranges epimere beds and lower section catalyst bed, on the housing between epimere beds and the lower section catalyst bed back with water inlet line is set.
Between described epimere beds and the lower section catalyst bed packing layer can be set, packing layer is positioned at the below of back with water inlet line entry position.Back with water inlet line is positioned at the reactor middle part, is positioned at 35% ~ 65% scope of reactor virtual height.
H
1/ (H
1+ H
2)=20% ~ 80%, wherein H
1Be the height of epimere beds, H
2Height for the lower section catalyst bed.The height that is the epimere beds is 20% ~ 80% of epimere beds and lower section catalyst bed total height.
The effect of back with water inlet line is when bed temperature exceeds the use temperature of reactor or catalyzer, spray into the vapour-liquid mixture of liquid water, water vapour or water and water vapor in the reactor, the adding mode of water adopts the spray mode to add, and preferably adopts the sprinkling equipments such as shower nozzle to add with uniform forms such as atomizings.
The effect of packing layer is so that water, the especially liquid water that adds by back with water inlet line or the vapour-liquid mixture of water and water vapor, and fully mixes from the process gas of epimere beds, and liquid water substantially is gasified totally and enters the lower section catalyst bed again.Filler in the packing layer is Raschig ring, Pall ring, structured packing, alumina ball and other large specific surfaces, can satisfies the material that the gas-liquid two-phase medium fully contacts.Bed stuffing height is generally 0.3 ~ 2 meter, is advisable so that liquid water is gasified totally.
When the water of back with water inlet line adding mainly is water vapour, can be without packing layer, directly adding gets final product.The preferred saturated steam that adopts under the conversion pressure.When the water that adds was mainly liquid water, because the latent heat of vaporization of water is very large, a small amount of water just can reach the purpose of cooling; When the water that adds was mainly water vapour, although cooling-down effect can save packing layer not as liquid water, equipment was simple, invest lowly, spent or during as emergency schedule, preferably added water vapour when only reducing by tens to temperature.
The present invention adds entry between upper and lower section beds, reduce bed temperature with easy mode, has improved simultaneously water-gas ratio, also is conducive to improve the interconversion rate of CO.
The present invention adopts water vapour and high-concentration carbon monoxide reaction, is applied to the production of oxo-synthesis gas, hydrogeneous gas mixture.
The sulfur resistant conversion process of described reactor has following dual mode:
(1) process gas enters into reactor by admission line, through the transformationreation of epimere beds, with after the water that is entered by water pipeline mixes, enters at last the lower section catalyst bed and carries out transformationreation again;
(2) process gas enters into reactor by admission line, after the transformationreation of epimere beds, again with the water that is entered by water pipeline mix be incorporated in packing layer and fully contact after, enter at last the lower section catalyst bed and carry out transformationreation.
The processing condition of epimere beds entrance: water/gas volume ratio 0.6 ~ 1.6, dry gas air speed 2000 ~ 12000h
-1, 220 ~ 300 ℃ of temperature ins;
The processing condition of lower section catalyst bed entrance: water/gas volume ratio 0.2 ~ 0.8, dry gas air speed 2000 ~ 12000h
-1, 260 ~ 400 ℃ of temperature ins.
The present invention has following beneficial effect:
(1) the invention provides a kind of high concentration CO sulfur-tolerant water gas shift device and sulfur resistant conversion process of not adjusting from the water-gas ratio of gasification unit process gas own, steam consumption is low; Pre-reactor and interchanger need not be set; Can avoid occuring the danger of methanation reaction; Prevent that effectively the shift-converter bed temperature is too high, and the heat that shift-converter inner conversion reaction is produced is fully used;
(2) the present invention adopts the method that adds water for cooling between the upper-lower section beds, and process is simple, and equipment is few, not only lowers the temperature but also improved water-gas ratio, has reduced the thermal load of system, has saved steam consumption; The CO transformation efficiency is high.
(3) conversion process of the present invention need not adopt heat-exchange equipment, takes full advantage of the heat that reactor inner conversion reaction produces.
(4) the present invention is to the strong adaptability of Coal rank and gasifying process; Flexible and convenient operation has improved the throughput of equipment.
Description of drawings
Fig. 1 is the embodiment of the invention 1 ~ 2 structure of reactor schematic diagram;
Fig. 2 is the embodiment of the invention 3 structure of reactor schematic diagram;
Among the figure: 1, admission line; 2, reactor shell; 3, epimere beds; 4, packing layer; 5, lower section catalyst bed; 6, the pipeline of giving vent to anger; 7, back with water inlet line.
Embodiment
Below in conjunction with embodiment and accompanying drawing the present invention is described further.
Certain device adopts the GSP gasifying process, and producing the process gas flow is 131197Nm
3/ h, pressure 3.75MPa, water-gas ratio is 0.78, feed gas composition: CO:40.59%, CO
2: 2.52%, H
2: 12.72, H
2O:43.71%, H
2S+COS:0.13%.The butt of CO formed≤22% after requirement was reacted through the first shift-converter.
Described shift-converter, comprise reactor shell 2, reactor shell 2 tops arrange admission line 1, the bottom sets out gas pipeline 6, reactor shell 2 inside arrange epimere beds 3 and lower section catalyst bed 5, on the housing 2 between epimere beds 3 and the lower section catalyst bed 5 back with water inlet line 7 are set.Between epimere beds 3 and the lower section catalyst bed 5 packing layer 4 is set, packing layer 4 is positioned at the below of back with water inlet line 7 entry positions.
Table 1 embodiment 1 operating parameters
Gasification the process gas flow that produces, pressure, water-gas ratio, react through the first shift-converter after the butt composition requirement etc. of CO identical with embodiment 1.The shift-converter structure is identical with embodiment 1.
Adopt shift-converter of the present invention, epimere beds 3 filling 12m
3, lower section catalyst bed 5 filling 6m
3, epimere beds 3 height H
1With epimere beds 3 and lower section catalyst bed 5 total height (H
1+ H
2) ratio be 2/3; Described unstripped gas directly enters epimere beds 3, and temperature in is 250 ℃.Load alumina ball in the packing layer 4, loading height is 0.4 meter.Flow, the wet basis content of 3 outlets of epimere beds, lower section catalyst bed 5 entrances, lower section catalyst bed 5 outlets form, add liquid water (temperature is 150 ℃) amount and with the conventional axial reactor relatively see Table 2.
Table 2 embodiment 2 operating parameterss
Gasification the process gas flow that produces, pressure, water-gas ratio, react through the first shift-converter after the butt composition requirement etc. of CO identical with embodiment 1.
Described shift-converter, comprise reactor shell 2, reactor shell 2 tops arrange admission line 1, the bottom sets out gas pipeline 6, reactor shell 2 inside arrange epimere beds 3 and lower section catalyst bed 5, on the housing 2 between epimere beds 3 and the lower section catalyst bed 5 back with water inlet line 7 are set.
Adopt shift-converter of the present invention, epimere beds 3 filling 9m
3, lower section catalyst bed 5 filling 9m
3, epimere beds 3 height H
1With epimere beds 3 and lower section catalyst bed 5 total height (H
1+ H
2) ratio be 1/2; Described unstripped gas directly enters epimere beds 3, and temperature in is 250 ℃.Do not establish packing layer 4.Flow, the wet basis content of 3 outlets of epimere beds, lower section catalyst bed 5 entrances, lower section catalyst bed 5 outlets form, add saturation steam (temperature is 250 ℃) amount and with the conventional axial reactor relatively see Table 3.
Table 3 embodiment 3 operating parameterss
From table 1 ~ 3, find out:
1) reactor of the present invention very easily operates, and outlet CO content (butt) can be regulated in 13% ~ 21% scope.Adopt the conventional axial reactor, when reaction finally reached balance, outlet CO content was the 18%(butt).
2) spray into water or water vapour in the middle of the reactor of the present invention, outlet process gas top temperature is 485 ℃, and minimum temperature is 440 ℃; There is not overheating problem fully.Use the conventional axial reactor, temperature out is up to 530 ℃, and is extremely unfavorable concerning catalyzer.
3) can spray into water or water vapour in the middle of the reactor of the present invention, improve the CO transformation efficiency.
As seen, reactor of the present invention can prevent effectively that the shift-converter bed temperature is too high, and the heat that shift-converter inner conversion reaction is produced is fully used.
Claims (7)
1. sulfur-tolerant water gas shift device that is used for high concentration CO, comprise reactor shell (2), it is characterized in that: reactor shell (2) top arranges admission line (1), the bottom sets out gas pipeline (6), reactor shell (2) inside arranges epimere beds (3) and lower section catalyst bed (5), on the housing (2) between epimere beds (3) and the lower section catalyst bed (5) back with water inlet line (7) is set.
2. the sulfur-tolerant water gas shift device for high concentration CO according to claim 1, it is characterized in that: between described epimere beds (3) and the lower section catalyst bed (5) packing layer (4) is set, packing layer (4) is positioned at the below of back with water inlet line (7) entry position.
3. the sulfur-tolerant water gas shift device for high concentration CO according to claim 1 and 2 is characterized in that: the height of described epimere beds (3) is epimere beds (3) and 20% ~ 80% of lower section catalyst bed (5) total height.
4. sulfur resistant conversion process that adopts the described reactor of claim 1, it is characterized in that: process gas enters into reactor by admission line (1), through epimere beds (3) transformationreation, with after the water that is entered by back with water inlet line (7) mixes, enter at last lower section catalyst bed (5) and carry out transformationreation again;
The processing condition of epimere beds (3) entrance: water/gas volume ratio 0.6 ~ 1.6, dry gas air speed 2000 ~ 12000h
-1, 220 ~ 300 ℃ of temperature ins;
The processing condition of lower section catalyst bed (5) entrance: water/gas volume ratio 0.2 ~ 0.8, dry gas air speed 2000 ~ 12000h
-1, 260 ~ 400 ℃ of temperature ins.
5. the sulfur resistant conversion process of described reactor according to claim 4, it is characterized in that: described process gas enters into reactor by admission line (1), after epimere beds (3) transformationreation, again with the water that is entered by back with water inlet line (7) mix be incorporated in packing layer (4) and fully contact after, enter at last lower section catalyst bed (5) and carry out transformationreation.
6. according to claim 4 or the sulfur resistant conversion process of 5 described reactors, it is characterized in that: described water is the vapour-liquid mixture of liquid water, water vapour or water and water vapor.
7. the sulfur resistant conversion process of described reactor according to claim 6, it is characterized in that: the adding mode of described water adopts the spray mode to add.
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| CN2012102906505A CN102910583A (en) | 2012-08-15 | 2012-08-15 | Sulfur-tolerance shift reactor and sulfur-tolerance shift process for high-concentration CO |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104176705A (en) * | 2014-08-08 | 2014-12-03 | 山东齐鲁科力化工研究院有限公司 | Sulfur-resisting conversion process for producing synthesis gas |
| US10406478B2 (en) | 2017-05-25 | 2019-09-10 | Jiangnan Environmental Protection Group Inc. | Ammonia-based desulfurization process and apparatus |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN201807347U (en) * | 2010-09-30 | 2011-04-27 | 胶州市科大催化技术服务中心 | Reactor for performing shift reaction of high-concentration CO raw gas |
| CN202717578U (en) * | 2012-08-15 | 2013-02-06 | 山东齐鲁科力化工研究院有限公司 | Sulphur-resistant conversion reactor for high-concentration carbon monoxide (CO) |
-
2012
- 2012-08-15 CN CN2012102906505A patent/CN102910583A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN201807347U (en) * | 2010-09-30 | 2011-04-27 | 胶州市科大催化技术服务中心 | Reactor for performing shift reaction of high-concentration CO raw gas |
| CN202717578U (en) * | 2012-08-15 | 2013-02-06 | 山东齐鲁科力化工研究院有限公司 | Sulphur-resistant conversion reactor for high-concentration carbon monoxide (CO) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104176705A (en) * | 2014-08-08 | 2014-12-03 | 山东齐鲁科力化工研究院有限公司 | Sulfur-resisting conversion process for producing synthesis gas |
| CN104176705B (en) * | 2014-08-08 | 2016-05-25 | 山东齐鲁科力化工研究院有限公司 | A kind of sulfur resistant conversion process of producing synthesis gas |
| US10406478B2 (en) | 2017-05-25 | 2019-09-10 | Jiangnan Environmental Protection Group Inc. | Ammonia-based desulfurization process and apparatus |
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Application publication date: 20130206 |