CN213569530U - System for preparing ethanol and ethylene glycol synthesis gas through coke-oven gas carbon return conversion and by-producing hydrogen - Google Patents
System for preparing ethanol and ethylene glycol synthesis gas through coke-oven gas carbon return conversion and by-producing hydrogen Download PDFInfo
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- CN213569530U CN213569530U CN202022764877.1U CN202022764877U CN213569530U CN 213569530 U CN213569530 U CN 213569530U CN 202022764877 U CN202022764877 U CN 202022764877U CN 213569530 U CN213569530 U CN 213569530U
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Abstract
The utility model discloses a system for coke-oven gas returns carbon conversion system ethanol, ethylene glycol synthetic gas and by-product hydrogen belongs to coke-oven gas system synthetic gas technical field. The system of the utility model comprises a coke oven gas deoiling and decalcification unit, a coke oven gas heating unit, a coke oven gas hydrodesulfurization unit, a coke steaming mixed gas heating unit, a pure oxygen conversion unit, a conversion gas heat recovery unit, a conversion gas cooling unit, a conversion gas water separation unit, a conversion gas decarbonization unit, a PSA-CO unit and a PSA-H unit which are connected in sequence2A unit; also includes returning CO2A compression unit, a reformed gas decarbonization unit, a return CO2The compression unit and the coke steaming mixed gas heating unit generate heat along the converted gas decarburization unitThe airflow directions of the formed decarburization regeneration gases are connected in sequence. The utility model discloses the regeneration gas CO of gas decarbonization will be transformed2After compression, returning to be converted to obtain CO and H meeting the requirements of ethanol and ethylene glycol synthesis2With exception, there is a surplus of H2Can be sold or used as raw material for producing other chemical products.
Description
Technical Field
The utility model belongs to the technical field of the coke-oven gas system synthetic gas, concretely relates to coke-oven gas returns carbon conversion system ethanol or for ethylene glycol synthetic gas and by-product hydrogen system.
Background
When a general coking enterprise produces metallurgical coke, the typical composition of coke oven gas is as follows:
| components | H2 | CO2 | CO | N2 | CH4 | CmHn | O2 | Total up to |
| Content (V%) | 59.7 | 2.8 | 7.5 | 5.0 | 21.9 | 2.3 | 0.8 | 100.00 |
The impurity content is as follows:
| components | H2S | Organic sulfur | Naphthalene | Tar plus dust | NH3 | B.T.X (benzene) | HCN |
| Content (mg/Nm)3) | ≤20 | ≤150 | ≤100 | ≤50 | ≤50 | ≤3000 | ≤100 |
Coke oven gas contains a large amount of CH4And H2Can be substituted by CH4Conversion to CO, CO2And H2Removal of CO2After separation, CO and H can be obtained2Except CO and H required for synthesizing ethanol and ethylene glycol2In addition to the ratio requirements, there is also excess H2Can be sold or used as raw material for producing other chemical products. In order to obtain more CO, the regeneration gas CO obtained by decarbonizing the conversion gas2And returning to conversion for recycling after compression.
Therefore, the system for preparing the synthesis gas for ethanol or ethylene glycol by coke oven gas carbon return conversion and by-producing hydrogen is a problem to be solved by the technical personnel in the field.
SUMMERY OF THE UTILITY MODEL
One of the purposes of the utility model is to provide a system for producing synthesis gas and hydrogen by-product by coke oven gas carbon-returning conversion, and CO and H meeting the requirements of ethanol or glycol can not only be produced by adopting the system2And hydrogen can be produced as a by-product.
In order to achieve the above object, the utility model adopts the following technical scheme:
the utility model discloses a system for coke-oven gas returns carbon conversion system synthetic gas and by-product hydrogen, including coke-oven gas deoiling decalcification unit, coke-oven gas heating unit, coke-oven gas hydrodesulfurization unit, evaporate burnt gas mixture heating unit, pure oxygen conversion unit, conversion gas heat recovery unit, conversion gas cooling unit, conversion gas water separating unit, conversion gas decarbonization unit, PSA-CO unit and PSA-H unit that connect gradually2A unit; also includes returning CO2A compression unit, a reformed gas decarbonization unit, a return CO2The compression unit and the coke steaming mixed gas heating unit are sequentially connected along the airflow direction of the decarbonization regenerated gas generated by the converted gas decarbonization unit.
In some embodiments of the present invention, the system further comprises a TSA purification unit; the converted gas decarbonization unit, the TSA purification unit and the PSA-CO unit are connected in sequence.
In some embodiments of the utility model, the coke oven gas deoiling and decalcifying unit is connected with a raw material gas conveying pipe for inputting coke oven gas to the coke oven gas deoiling and decalcifying unit;
the coke steaming mixed gas heating unit is connected with a medium-pressure steam conveying pipe for inputting steam to the coke steaming mixed gas heating unit; the pure oxygen conversion unit is connected with an oxygen evaporation mixed gas conveying pipe for inputting oxygen evaporation mixed gas into the pure oxygen conversion unit.
In some embodiments of the utility model, the coke oven gas heating unit, the coke oven gas deoiling and decalcification unit and the coke oven gas hydrodesulfurization unit are respectively connected through a deoiling and decalcification gas conveying pipe and a heating gas conveying pipe;
a coke steaming mixed gas heating unit, a coke oven gas hydrodesulfurization unit, a pure oxygen conversion unit and a return CO2The compression unit passes through a desulfurization gas delivery pipe, a heating coke-steaming mixed gas delivery pipe and CO respectively2The compressed air conveying pipe is connected.
In some embodiments of the utility model, the converted gas heat recovery unit is connected with the pure oxygen conversion unit and the converted gas cooling unit through the high-temperature converted gas conveying pipe and the first cooling converted gas conveying pipe respectively;
the reformed gas-water separation unit is connected with the reformed gas cooling unit and the reformed gas decarburization unit through a second cooling reformed gas conveying pipe and a drying reformed gas conveying pipe respectively.
In some embodiments of the invention, the reformed gas decarbonization unit and the return CO2The compression unit and the TSA purification unit are respectively connected through a regenerated gas conveying pipe and a first decarburization conversion gas conveying pipe;
PSA-CO unit, TSA purification unit, PSA-H2The units are respectively connected with a second decarburization and reforming gas conveying pipe and a crude hydrogen conveying pipe.
In some embodiments of the present invention, the PSA-CO unit is connected to a CO discharge pipe for inputting CO for synthesis to the ethanol synthesis apparatus or the ethylene glycol synthesis apparatus;
PSA-H2the unit is connected with a device for inputting H for synthesis to an ethanol synthesis device or an ethylene glycol synthesis device2First H of2Discharge pipe for discharging by-product H2Second H of2A discharge pipe and a hydrogen extraction suction gas discharge pipe.
The utility model discloses an among the partial embodiment, coke-oven gas deoiling and decalcification unit is including the coke-oven gas preprocessing device, coke-oven gas compressor arrangement, the coke-oven gas secondary deoiling and decalcification device that connect gradually.
In some embodiments of the utility model, the coke oven gas pretreatment device is connected with the feed gas conveying pipe;
the coke-oven gas secondary deoiling and naphthalene removing device is connected with the coke-oven gas heating unit through a deoiling and naphthalene removing gas conveying pipe;
the coke-oven gas compression device is connected with the coke-oven gas pretreatment device and the coke-oven gas secondary deoiling and decalcification device through a pretreatment gas conveying pipe and a compressed gas conveying pipe respectively.
In some embodiments of the present invention, one end of the oxygen-steam mixed gas delivery pipe is connected to the pure oxygen conversion unit, and the other end is connected to the oxygen delivery pipe and the superheated steam delivery pipe.
The utility model discloses a method of coke-oven gas carbon supplementation conversion system ethanol, synthetic gas for ethylene glycol, this method adopts foretell system to go on, include following step:
step 1, introducing the coke-oven gas into a coke-oven gas deoiling and decalcification unit, removing tar and naphthalene, then introducing the coke-oven gas into a coke-oven gas heating unit, heating, and then introducing the coke-oven gas into a coke-oven gas hydrodesulfurization unit to remove sulfur in the coke-oven gas;
step 2, feeding the medium-pressure steam, the decarbonized regenerated gas and the coke-oven gas desulfurized in the step 1 into a coke-steaming mixed gas heating unit for heating to form coke-steaming mixed gas, and heating to the temperature required by pure oxygen conversion;
and 3, feeding the coke steaming mixed gas heated in the step 2 into a pure oxygen conversion unit, mixing the coke steaming mixed gas with superheated steam and oxygen which are supplemented from outside to form a steam oxygen mixed gas, and carrying out oxidation and conversion reaction under the action of a conversion catalyst to generate H-containing gas2CO and CO2The converted gas of (3);
step 4, the converted gas generated in the step 3 enters a converted gas heat recovery unit to recover the heat contained in the converted gas, and the converted gas added with the heat is cooled in a converted gas cooling unit;
step 5, the reformed gas cooled in the step 4 enters a reformed gas-water separation unit, and free water in the reformed gas is separated;
step 6, the converted gas with the free water separated in the step 5 enters a converted gas decarbonization unit to remove CO in the converted gas2To obtain decarbonized converted gas;
step 7, the decarbonized converted gas enters a PSA-CO unit, CO is obtained by pressure swing adsorption, and the obtained CO is sent to an ethanol or ethylene glycol synthesis device;
step 8, the converted gas with CO removed enters PSA-H2Unit for obtaining H by pressure swing adsorption2(ii) a Moiety H2Sending to an ethanol or ethylene glycol synthesis device; the rest hydrogen is sold or used as raw material for producing other chemical products.
In the step 1, introducing the coke-oven gas into a coke-oven gas pretreatment device, adsorbing and removing part of tar and naphthalene in the coke-oven gas, and then introducing the coke-oven gas into a coke-oven gas compression device for gas compression; the compressed gas enters a coke-oven gas secondary deoiling and naphthalene removing device to remove residual tar and naphthalene, and enters a coke-oven gas heating unit after the tar and the naphthalene are removed;
preferably, in the step 1, the coke oven gas is introduced into a coke oven gas pretreatment device, a carbon-based adsorbent with strong adsorption capacity to tar and naphthalene in the coke oven gas is adopted to adsorb the tar and the naphthalene in the coke oven gas, then the coke oven gas is purged and regenerated once by steam at intervals, and the regenerated wastewater is subjected to coking treatment; in the coke oven gas compression device, a reciprocating compressor, a screw compressor and a centrifugal compressor can be adopted for compression, and the pressure of the compressed coke oven gas is 0.8-6.0 MPa; the compressed coke-oven gas still contains a small amount of naphthalene, oil, water and other impurities, and the coke-oven gas is further finely removed by adopting a carbon-based complexing agent, a silicate complexing agent and the like in a secondary deoiling and decalcification device so as to reduce the influence on the subsequent processes. The carbon-based complexing agent and the silicate complexing agent after adsorbing the oil and the naphthalene are regenerated once by steam blowing at intervals according to the operation working conditions, and the regenerated wastewater is subjected to coking treatment.
The coke-oven gas after compression, deoiling and decalcification enters a coke-oven gas heating unit, and in the coke-oven gas heating unit, the coke-oven gas is heated to the temperature required by the hydrodesulfurization of the coke-oven gas by using the hydrogen extracting and desorbing gas as fuel.
The heated coke oven gas enters a coke oven gas hydrodesulfurization unit according to inorganic sulfur (H) in the coke oven gas2S) is mostly removed, but the content of organic sulfur (sulfur oxygen carbon, carbon disulfide, mercaptan, thioether, thiophene and the like) is more, and the organic sulfur is subjected to pre-hydrogenation and primary hydrogenation by a solid catalyst to be converted into inorganic sulfur (H)2S), removing the generated inorganic sulfur (H) by a solid desulfurizing agent2S), and then carrying out secondary hydrogenation to convert the residual organic sulfur into inorganic sulfur (H)2S) and removing the sulfur by a solid desulfurizer until the total sulfur in the coke oven gas is removed to be less than or equal to 0.1 ppm.
In the step 2, supplementing the coke-oven gas subjected to hydrodesulfurization with medium-pressure steam and decarbonization regeneration gas to form coke-steaming mixed gas, heating the converted gas subjected to steam generation to a certain temperature, then feeding the heated gas into a coke-steaming mixed gas heating furnace, and heating the coke-steaming mixed gas to a temperature required by pure oxygen conversion by using hydrogen extraction gas as fuel;
in step 3, superheated steam and oxygen are mixed according to a certain proportion to form steam-oxygen mixed gas, the steam-oxygen mixed gas enters a pure oxygen reformer burner and is used as a reforming catalyst together with high-temperature coke-steaming mixed gas entering simultaneouslyOxidation and conversion reaction are carried out under the condition of generating H2CO and CO2Converted gas of (CH)4The content of the active carbon is reduced to below 0.5 percent, and the outlet temperature reaches about 1000 ℃;
in the step 4, the reformed gas generated in the step 3 at about 1000 ℃ is subjected to heat recovery and conversion, and specifically, the heat contained in the reformed gas can be recovered through medium-pressure steam generated by a steam generator, heating of a coke-steam mixed gas by a coke-steam heater, preheating of drum feed water, heating of a reboiler of a decarburization regeneration tower as a heat source, heating of refrigeration cycle hot water and the like;
the converted gas after heat recovery is cooled to be less than or equal to 40 ℃ by water cooling or air cooling and water cooling.
In the step 5, the reformed gas cooled to less than or equal to 40 ℃ is subjected to two-stage water separation to basically separate free water in the reformed gas.
In some embodiments of the present invention, in step 6, the decarbonizing solution after pressure swing adsorption or regeneration is used to convert CO in the gas2Removing; the desorbed gas of pressure swing adsorption decarburization or the decarbonized regenerated gas generated by heating and regenerating the decarbonization liquid is returned to CO2The compressed coke enters a coke steaming mixed gas heating unit for cyclic utilization;
preferably, in step 6, the decarbonized converted gas passes through a TSA purification unit, and after moisture and a small amount of other impurities in the decarbonized converted gas are removed by temperature swing adsorption, the decarbonized converted gas enters a PSA-CO unit.
In step 7, Pressure Swing Adsorption (PSA) technology is utilized to make CO in the decarbonized converted gas mainly adsorbed by the adsorbent, then through a series of adsorption steps, the adsorbed CO is desorbed through reverse discharge and evacuation, the gas obtained through reverse discharge and evacuation is used as CO product, and the CO product is sent to an ethanol and ethylene glycol synthesis device after being compressed;
in step 8, the Pressure Swing Adsorption (PSA) technology is used to remove H from the CO-extracted gas2Other components are adsorbed by the adsorbent, and then through a series of adsorption steps, the adsorbed impurities are desorbed through reverse release and evacuation, and the hydrogen is extracted and sucked to remove coke oven gas for heating, the coke-steaming mixed gas for heating and steam superheating as fuels; the unadsorbed passing gas is H2Product, sent toAlcohol and ethylene glycol synthesizing device; excess H2Sold or used as raw material for producing other chemical products.
Compared with the prior art, the utility model discloses following beneficial effect has:
the utility model relates to a rationally, simple structure, convenient operation. The invention is the regeneration gas CO for decarbonizing the conversion gas2After compression, returning to be converted to obtain CO and H meeting the requirements of ethanol and ethylene glycol synthesis2With exception, there is a surplus of H2Can be sold or used as raw material for producing other chemical products.
Drawings
FIG. 1 is a system diagram of the present invention for producing synthetic gas and by-producing hydrogen by coke oven gas carbon-returning conversion.
Wherein, the names corresponding to the reference numbers are:
1-medium pressure steam conveying pipe, 2-raw gas conveying pipe, 3-pretreatment gas conveying pipe, 4-compressed gas conveying pipe, 5-deoiling and decalcification gas conveying pipe, 6-heating gas conveying pipe, 7-desulfurization gas conveying pipe, 8-heating and coking mixed gas conveying pipe, 9-steam oxygen mixed gas conveying pipe, 10-oxygen conveying pipe, 11-superheated steam conveying pipe, 12-high temperature reformed gas conveying pipe, 13-first cooling reformed gas conveying pipe, 14-second cooling reformed gas conveying pipe, 15-drying reformed gas conveying pipe, 16-regeneration gas conveying pipe, 17-first decarburization reformed gas conveying pipe, 18-second decarburization reformed gas conveying pipe, 19-crude hydrogen conveying pipe, 20-CO discharging pipe, 21-first H gas conveying pipe2Tapping pipe, 22-second H2Tapping pipe, 23-CO2A compressed gas conveying pipe and a 24-extraction hydrogen suction gas discharging pipe.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more clearly understood, the present invention is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
As shown in the attached figure 1, the embodiment provides the coke oven gas carbon return conversion systemThe system for the synthesis gas for the ethanol or the ethylene glycol comprises a coke-oven gas deoiling and decalcification unit, a coke-oven gas heating unit, a coke-oven gas hydrodesulfurization unit, a coke-steaming mixed gas heating unit, a pure oxygen conversion unit, a conversion gas heat recovery unit, a conversion gas cooling unit, a conversion gas water separation unit, a conversion gas decarbonization unit, a PSA-CO unit and a PSA-H unit which are sequentially connected2A unit; also includes returning CO2A compression unit, the converted gas decarbonization unit, the return CO2The compression unit and the coke steaming mixed gas heating unit are sequentially connected along the airflow direction of the decarbonization regenerated gas generated by the converted gas decarbonization unit.
The system of the utility model also comprises a TSA purification unit; the converted gas decarbonization unit, the TSA purification unit and the PSA-CO unit are sequentially connected.
The coke-oven gas deoiling and decalcification unit comprises a coke-oven gas pretreatment device, a coke-oven gas compression device and a coke-oven gas secondary deoiling and decalcification device which are sequentially connected. Wherein the coke-oven gas pretreatment device is connected with a raw material gas conveying pipe 2 for inputting coke-oven gas into the coke-oven gas pretreatment device; the coke-oven gas secondary deoiling and naphthalene removing device is connected with the coke-oven gas heating unit through a deoiling and naphthalene removing gas conveying pipe 5; the coke-oven gas compression device is connected with the coke-oven gas pretreatment device and the coke-oven gas secondary deoiling and decalcification device through a pretreatment gas conveying pipe 3 and a compressed gas conveying pipe 4 respectively.
The coke-oven gas heating unit is connected with the coke-oven gas hydrodesulfurization unit through a heating gas conveying pipe 6;
the coke steaming mixed gas heating unit is connected with a medium-pressure steam conveying pipe 1 for inputting steam to the coke steaming mixed gas heating unit; the coke steaming mixed gas heating unit, the coke oven gas hydrodesulfurization unit, the pure oxygen conversion unit and the return CO2The compression unit passes through a desulfurization gas delivery pipe 7, a heating and coke-steaming mixed gas delivery pipe 8 and a CO delivery pipe respectively2The compressed air conveying pipe 23 is connected;
the pure oxygen conversion unit is connected with one end of an oxygen evaporation mixed gas conveying pipe 9 for inputting oxygen evaporation mixed gas into the pure oxygen conversion unit, and the other end of the oxygen evaporation mixed gas conveying pipe 9 is connected with an oxygen conveying pipe 10 and a superheated steam conveying pipe 11 respectively.
The converted gas heat recovery unit is connected with the pure oxygen conversion unit and the converted gas cooling unit through a high-temperature converted gas conveying pipe 12 and a first cooling converted gas conveying pipe 13 respectively;
the converted gas-water separation unit is connected with the converted gas cooling unit and the converted gas decarbonization unit through a second cooled converted gas conveying pipe 14 and a dry converted gas conveying pipe 15 respectively.
The conversion gas decarbonization unit and the return CO2The compression unit and the TSA purification unit are respectively connected through a regenerated gas conveying pipe 16 and a first decarburization and transformation gas conveying pipe 17;
the PSA-CO unit, the TSA purification unit and the PSA-H2The units are respectively connected through a second decarburization conversion gas delivery pipe 18 and a crude hydrogen delivery pipe 19.
The PSA-CO unit is connected with a CO discharge pipe 20 for inputting CO for synthesis to an ethanol synthesis device or an ethylene glycol synthesis device;
the PSA-H2The unit is connected with a device for inputting H for synthesis to an ethanol synthesis device or an ethylene glycol synthesis device2First H of2Discharge pipe 21 for discharging byproduct H2Second H of2A tapping 22, and a stripping suction gas tapping 24.
Example 2
This example discloses the conversion of coke oven gas to ethanol, ethylene glycol syngas (CO and H)2) And a by-product hydrogen production process using the system of example 1 to produce 20 ten thousand tons of syngas (13800 Nm/N) required by the ethanol plant3CO and 25970Nm3/h H2) For example.
The coke oven gas entering the system has the pressure of 6-7 kPa, the normal temperature and the gas amount of 39000Nm3Composition is shown in the following table:
| components | H2 | CO2 | CO | N2 | CH4 | CmHn | O2 | Total up to |
| Content (V%) | 59.7 | 2.8 | 7.5 | 5.0 | 21.9 | 2.3 | 0.8 | 100.00 |
The impurity levels are shown in the following table:
| components | H2S | Organic sulfur | Naphthalene | Tar plus dust | NH3 | B.T.X (benzene) | HCN |
| Content (mg/Nm)3) | ≤20 | ≤150 | ≤100 | ≤50 | ≤50 | ≤3000 | ≤100 |
Firstly, adsorbing tar and naphthalene in the coke-oven gas by adopting a carbon-based adsorbent through a coke-oven gas pretreatment device, wherein in the pretreated coke-oven gas: tar plus dust less than or equal to 10mg/Nm3Naphthalene is less than or equal to 20mg/Nm3。
Then the coke oven gas enters a coke oven gas compression device, four-stage compression is carried out by adopting two reciprocating compressors, and the pretreated coke oven gas is compressed to 2.4 MPa. The compressed gas enters a coke oven gas secondary deoiling and decalcification device, a carbon-based complexing agent, a silicate complexing agent and the like are adopted to further deoil and decalcification, and the gas is in the coke oven gas after deoiling and decalcification: tar plus dust less than or equal to 1mg/Nm3Naphthalene is less than or equal to 2mg/Nm3。
The coke oven gas after deoiling and decalcification enters a coke oven gas heating unit, and in the coke oven gas heating unit, the coke oven gas is heated to-250 ℃ by using hydrogen extraction and desorption gas as fuel.
And the heated coke-oven gas enters a coke-oven gas hydrodesulfurization unit. In this example, a coke ovenThe gas hydrodesulfurization unit comprises a pre-hydrogenation tank, a primary fine desulfurization tank, a secondary hydrogenation tank and a secondary fine desulfurization tank. The two prehydrogenation tanks can be parallelly connected or individually used, mainly can hydrogenate and saturate unsaturated hydrocarbon in coke-oven gas, and can remove oxygen from the unsaturated hydrocarbon, at the same time, can make a small quantity of organic desulfurization and hydrogenation convert it into inorganic sulfur (H)2S). The coke oven gas after pre-hydrogenation enters a primary hydrogenation tank, organic desulfurization in the coke oven gas is further subjected to hydro-conversion, and then the coke oven gas enters a primary fine desulfurization tank which can be used in series, in parallel or independently for removing H generated by hydro-conversion2S; in order to further reduce organic sulfur and inorganic sulfur in the coke-oven gas, the coke-oven gas enters a secondary hydrogenation tank and two secondary fine desulfurization tanks. When the first stage hydrodesulfurization can meet the total sulfur requirement of the process, the coke oven gas bypasses the bypass (does not pass through the second stage hydrodesulfurization). At the moment, the total sulfur in the coke-oven gas is removed to be less than or equal to 0.1 ppm.
Adding 14.5t/h of medium pressure steam and 8630Nm of decarbonized regenerated gas into the hydrodesulfurized coke-oven gas3And h, forming a coke steaming mixed gas, and feeding the coke steaming mixed gas into a coke steaming mixed gas heating unit. The coke steaming mixed gas heating unit in the implementation comprises a heat exchanger and a coke steaming mixed gas heating furnace. The coke steaming mixed gas and the converted gas which is used for generating steam by the heat exchanger are heated to 400 ℃, then the coke steaming mixed gas enters the coke steaming mixed gas heating furnace, the hydrogen extracting and absorbing gas is used as fuel, and the coke steaming mixed gas is heated to 630 ℃.
6.2t/h superheated steam and 7700Nm3The oxygen is mixed to form steam oxygen mixed gas, the steam oxygen mixed gas enters a pure oxygen converter burner of a pure oxygen conversion unit, the 630 ℃ steam coke mixed gas simultaneously enters a pure oxygen converter, oxidation and conversion reaction are carried out under the action of a conversion catalyst, and H is generated2CO and CO2The outlet temperature of the pure oxygen reformer is about 990 ℃, and the reformed gas composition is shown as the following table:
the converted gas amount is: 94700Nm3/h。
The converted gas from the pure oxygen converter enters a converted gas heat recovery unit to recover heat. The reformed gas heat recovery unit in this embodiment is composed of a steam generator, a drum water preheater, a coke steaming heater of a coke steaming mixed gas heating unit, and a decarburization regeneration tower of a reformed gas decarburization unit. The reformed gas with the outlet temperature of the pure oxygen reformer of about 990 ℃ firstly passes through a steam generator to generate medium-pressure steam of about 42t/h, and is cooled to 470 ℃ by itself; then the coke enters a coke steaming heater to heat the coke steaming mixed gas, and the temperature is reduced to 360 ℃; then enters a drum water preheater to preheat drum feed water, and is cooled to 240 ℃; entering a reboiler of a decarburization regeneration tower as a heat source, and cooling to 150 ℃; heating the refrigeration circulating hot water, and cooling to 90 ℃.
Recovering heat, introducing 90 deg.C reformed gas into a reformed gas cooling unit for separating free water, cooling to 60 deg.C by an air cooler, and cooling to below 40 deg.C by a water cooler; the free water in the reformed gas is basically separated by two-stage water separation.
The converted gas at 40 ℃ enters a converted gas decarbonization unit, and in the embodiment, the converted gas decarbonization unit comprises an absorption tower and a decarbonization regeneration tower. And washing and absorbing by using a decarbonization solution by adopting a wet decarbonization absorption tower. After the converted gas is washed by the semi-barren solution and the barren solution, CO in the gas2The content is reduced to 0.005 percent, and the decarbonized solution with trace amount in the gas is separated and removed and then enters a TSA purification unit.
The rich liquid from the bottom of the absorption tower enters the top of the decarburization regeneration tower, is decompressed to 0.1MPa, and is stripped by steam from the lower part of the tower. CO stripped from the top of the decarbonization regeneration tower2Cooling the gas to below 40 ℃, and returning the separated condensate to the top of the decarburization regeneration tower to be used as reflux; cooling and separating the decarbonized regeneration gas (CO) from the decarbonized liquid2About 97% and 8630Nm of gas3H) to return CO2And the compression unit is compressed and pressurized to 2.4MPa, and returns to the coke steaming mixed gas heating unit for cyclic utilization.
The decarbonized semi-barren solution coming out from the bottom of the upper section of the decarbonization regeneration tower is divided into two parts. Most of the semi-barren solution is pressurized and then circulated to the middle part of the absorption tower; and the rest semi-barren solution is preheated and then sent to the lower section of the decarburization regeneration tower for continuous regeneration, and the decarburization barren solution from the bottom of the lower section of the decarburization regeneration tower is cooled and then sent to the upper part of the absorption tower for cyclic absorption. The heat of the reboiler of the decarburization regeneration tower is provided by the converted gas.
The decarburization converted gas comprises the following components:
| components | H2 | CO | CO2 | N2 | CH4 | H2O | O2 | Total up to |
| Content (%) | 67.1 | 28.4 | 0.005 | 3.7 | 0.4 | 0.4 | - | 100.00 |
The decarbonization conversion gas quantity is as follows: 53900Nm3/h。
53900Nm3The decarbonized converted gas enters a TSA purification unit, and the moisture and a small amount of other impurities in the decarbonized converted gas are removed by using a temperature swing adsorption technology.
And (4) introducing the decarbonized converted gas subjected to TSA purification treatment into a PSA-CO unit to extract CO. The PSA-CO unit consists of 12 adsorbers and a series of programmed valves. At any moment, the adsorber is always in different stages of the adsorption step, feed gas is introduced from the inlet end, and the adsorbed passing gas obtained from the outlet end is used as crude hydrogen to enter PSA-H2A unit; each adsorber undergoes adsorption (a), pressure Equalization (EiD), displacement (RP) reverse pressure release (D), vacuum (V), pressure Equalization (EiR), and final pressure boost (FR) in sequence at different times. The adsorbed CO is desorbed by reverse discharge and evacuation. The CO gas which is reversely discharged and pumped out is used as a product to be stabilized at 0.02MPa, and is sent to an ethanol synthesis device after being compressed. CO concentration of 98.9% and yield of 13800Nm3H is used as the reference value. Crude hydrogen from a PSA-CO unit is passed to PSA-H2A hydrogen extraction unit. PSA-H2The unit consists of 12 adsorbers and a series of programmed valves. At any moment, the adsorber is always in different stages of the adsorption step, feed gas is introduced from the inlet end, and product hydrogen is obtained at the outlet end; each adsorber undergoes adsorption (a), pressure Equalization (EiD), reverse pressure release (D), vacuum (V), pressure Equalization (EiR), and final pressure boost (FR) in sequence at different times. The adsorbed impurities are desorbed by reverse discharging and evacuating, and the extracted hydrogen is desorbed to be used as fuel for coke oven gas heating unit, coke steaming mixed gas heating unit and steam overheating. H obtained by the present unit299.95% concentration and 35080Nm total3/h, wherein 25970Nm3The reaction solution is sent to an ethanol synthesis device for the rest 9110Nm3And/h is sold or sent to be used as raw materials for producing other chemical products.
The above embodiment is only one of the preferred embodiments of the present invention, and should not be used to limit the protection scope of the present invention, but all the insubstantial changes or modifications made in the spirit and the idea of the main design of the present invention, the technical problems solved by the embodiment are still consistent with the present invention, and all should be included in the protection scope of the present invention.
Claims (10)
1. The system for preparing ethanol and ethylene glycol synthesis gas through coke-oven gas carbon return conversion and hydrogen byproduct is characterized by comprising a coke-oven gas deoiling and decalcification unit, a coke-oven gas heating unit, a coke-oven gas hydrodesulfurization unit, a coke-steaming mixed gas heating unit, a pure oxygen conversion unit, a conversion gas heat recovery unit, a conversion gas cooling unit, a conversion gas water separation unit, a conversion gas decarbonization unit, a PSA-CO unit and a PSA-H unit which are sequentially connected2A unit; also includes returning CO2A compression unit, the converted gas decarbonization unit, the return CO2The compression unit and the coke steaming mixed gas heating unit are sequentially connected along the airflow direction of the decarbonization regenerated gas generated by the converted gas decarbonization unit.
2. The system of claim 1, further comprising a TSA purification unit; the converted gas decarbonization unit, the TSA purification unit and the PSA-CO unit are sequentially connected.
3. The system according to claim 1 or 2, characterized in that the coke oven gas deoiling and decalcifying unit is connected with a raw gas conveying pipe (2) to which coke oven gas is input;
the coke steaming mixed gas heating unit is connected with a medium-pressure steam conveying pipe (1) for inputting steam to the coke steaming mixed gas heating unit; the pure oxygen conversion unit is connected with an oxygen evaporation mixed gas conveying pipe (9) for inputting oxygen evaporation mixed gas into the pure oxygen conversion unit.
4. The system according to claim 1 or 2, wherein the coke oven gas heating unit is connected with the coke oven gas deoiling and naphthalene removing unit and the coke oven gas hydrodesulfurization unit through a deoiling and naphthalene removing gas conveying pipe (5) and a heating gas conveying pipe (6) respectively;
the coke steaming mixed gas heating unit, the coke oven gas hydrodesulfurization unit, the pure oxygen conversion unit and the return CO2The compression unit heats and evaporates the coke mixed gas through a desulfurization gas delivery pipe (7) respectivelyA delivery pipe (8), CO2The compressed air conveying pipes (23) are connected.
5. The system according to claim 1 or 2, wherein the reformed gas heat recovery unit and the pure oxygen conversion unit and the reformed gas cooling unit are respectively connected through a high-temperature reformed gas conveying pipe (12) and a first cooling reformed gas conveying pipe (13);
the converted gas-water separation unit is connected with the converted gas cooling unit and the converted gas decarbonization unit through a second cooled converted gas conveying pipe (14) and a dry converted gas conveying pipe (15) respectively.
6. The system of claim 2, wherein the reformed gas decarbonization unit and the return CO2The compression unit and the TSA purification unit are respectively connected through a regenerated gas conveying pipe (16) and a first decarburization and transformation gas conveying pipe (17);
the PSA-CO unit, the TSA purification unit and the PSA-H2The units are respectively connected through a second decarburization conversion gas delivery pipe (18) and a crude hydrogen delivery pipe (19).
7. The system according to claim 1 or 2, wherein the PSA-CO unit is connected with a CO outlet pipe (20) for feeding CO for synthesis to an ethanol synthesis plant or a glycol synthesis plant;
the PSA-H2The unit is connected with a device for inputting H for synthesis to an ethanol synthesis device or an ethylene glycol synthesis device2First H of2A discharge pipe (21) for discharging a by-product H2Second H of2A tapping pipe (22) and a stripping suction gas tapping pipe (24).
8. The system of claim 1, wherein the coke oven gas deoiling and naphthalene removing unit comprises a coke oven gas pretreatment device, a coke oven gas compression device and a coke oven gas secondary deoiling and naphthalene removing device which are connected in sequence.
9. The system according to claim 8, characterized in that the coke oven gas pre-treatment plant is connected with a feed gas conveying pipe (2);
the coke-oven gas secondary deoiling and naphthalene removing device is connected with the coke-oven gas heating unit through a deoiling and naphthalene removing gas conveying pipe (5);
the coke-oven gas compression device is connected with the coke-oven gas pretreatment device and the coke-oven gas secondary deoiling and decalcification device through a pretreatment gas conveying pipe (3) and a compressed gas conveying pipe (4) respectively.
10. The system according to claim 3, wherein the steam-oxygen mixture delivery pipe (9) is connected with a pure oxygen conversion unit at one end and with an oxygen delivery pipe (10) and a superheated steam delivery pipe (11) at the other end.
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|---|---|---|---|
| CN202022764877.1U CN213569530U (en) | 2020-11-25 | 2020-11-25 | System for preparing ethanol and ethylene glycol synthesis gas through coke-oven gas carbon return conversion and by-producing hydrogen |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202022764877.1U CN213569530U (en) | 2020-11-25 | 2020-11-25 | System for preparing ethanol and ethylene glycol synthesis gas through coke-oven gas carbon return conversion and by-producing hydrogen |
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| CN213569530U true CN213569530U (en) | 2021-06-29 |
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