CN208562273U - The device of coke-stove gas and converter and/or blast furnace gas synthesizing glycol coproduction LNG - Google Patents

The device of coke-stove gas and converter and/or blast furnace gas synthesizing glycol coproduction LNG Download PDF

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CN208562273U
CN208562273U CN201821189001.5U CN201821189001U CN208562273U CN 208562273 U CN208562273 U CN 208562273U CN 201821189001 U CN201821189001 U CN 201821189001U CN 208562273 U CN208562273 U CN 208562273U
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gas
hydrogenator
converter
blast furnace
reactor
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杨勇
戴乐亭
汪武平
侯俊平
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Shanxi Wex Chemical Technology Co ltd
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Abstract

Coke-stove gas and converter and/or blast furnace gas synthesizing glycol coproduction LNG device, including coke oven gas purifying device, converter and/or blast furnace gas purification plant, the decarbonization device of the thick decarbonization device of pressure-variable adsorption, coke-stove gas and converter and/or blast furnace gas, cryogenic separation device, CO purifying plant, H2Purifying plant, DMO synthesizer and ethylene glycol synthesizer;The device of the utility model.The device of the coke-stove gas of the utility model and converter and/or blast furnace gas synthesizing glycol coproduction LNG, make full use of the tail gas generated in coking and steelmaking process, lack H using blast furnace gas, the more CO of coal gas of converter2With oven gas more CH4, H2The characteristics of few CO, rationally purification and proportion, make effective gas (CO, H in gas2、CH4) 100% utilization, efficiently making full use of for resource may be implemented, reduce the wasting of resources and the pollution to environment, combine the high-quality high-end fine chemical product of output for steel and Chemical Engineering unit and open up the beginning.

Description

The device of coke-stove gas and converter and/or blast furnace gas synthesizing glycol coproduction LNG
Technical field
The utility model relates to field of gas purification, and in particular to a kind of to utilize coke-stove gas and converter and/or blast furnace coal The device of gas synthesizing glycol coproduction LNG.
Background technique
Coke-stove gas is also known as oven gas, refer to coal for coking in coke oven after high-temperature retorting, in output coke and coke Generated a kind of imflammable gas while oil product, is the byproduct of coking industry.The calorific value of coke-stove gas is higher, usually Fuel or town gas as high temperature industrial furnace.
As environmental requirement is gradually increased, the utilization rate of new coking industry permit standard clear stipulaties coke-stove gas is wanted More than 98%, while coking industry recessed market, excess capacity is serious, and people come to realise the huge exploitation value of coke-stove gas Value, therefore many coke-stove gas utilization technologies are had developed, such as coke-stove gas preparing liquefied natural gas, coke-stove gas methanol etc..
However, the main component of coke-stove gas is hydrogen and methane, there are also a small amount of carbon monoxide, carbon dioxide, nitrogen etc. Component has the characteristics that " hydrogen-rich lacks carbon ".In addition, coal gas of converter and blast furnace gas have that rich carbon lacks hydrogen, industry at present In turn out a produce only with pure gas, will lead to part active principle in gas in this way cannot make full use of, adjust Property it is poor, the tail gas containing part active principle need to separately find a way out or can only be used as fuel, cause energy waste and environment dirty Dye.
Utility model content
The technology of the utility model solves the problems, such as: overcome the deficiencies of the prior art and provide it is a kind of using coke-stove gas with The device of converter and/or blast furnace gas synthesizing glycol coproduction LNG.
The technical solution of the utility model is: a kind of coke-stove gas and converter and/or blast furnace gas synthesizing glycol Coproduction LNG device, including coke oven gas purifying device, converter and/or blast furnace gas purification plant, the thick decarburization dress of pressure-variable adsorption It sets, the decarbonization device of coke-stove gas and converter and/or blast furnace gas, cryogenic separation device, CO purifying plant, H2Purifying plant, DMO synthesizer and ethylene glycol synthesizer;
Coke oven gas purifying device includes sequentially connected dedusting detar device, compressor, desulfurizer, TSA absorption Device, compressor and deoxygenation fine de-sulfur device;
Converter and/or blast furnace gas purification plant include sequentially connected dedusting detar device, compressor, TSA absorption Device and deoxygenation fine de-sulfur device;
The outlet of deoxygenation fine de-sulfur device in converter and/or blast furnace gas purification plant and the thick decarbonization device of pressure-variable adsorption Entrance connection;
The outlet of deoxygenation fine de-sulfur device in coke oven gas purifying device and the outlet of the thick decarbonization device of pressure-variable adsorption Connect with the decarbonization device of coke-stove gas and converter and/or blast furnace gas, coke-stove gas and converter and/or blast furnace gas it is de- The coke-stove gas decarburization gas vent of carbon device successively connects with CO purifying plant, DMO synthesizer and ethylene glycol synthesizer It connects, the converter of the decarbonization device of coke-stove gas and converter and/or blast furnace gas and/or blast furnace gas decarburization gas vent and deep cooling Separator connection, the coke-stove gas decarburization gas outlet of the CO outlet and decarbonization device of cryogenic separation device, deep cooling point H from device2Outlet successively with H2Purifying plant is connected with ethylene glycol synthesizer.
Further, the thick decarbonization device of pressure-variable adsorption includes gas-liquid separator, adsorption tower group, and purified gas surge tank is pressed Tank, vacuum pump, coal gas supply road, vacuumize road, and purified gas buffers road, the road Jun Ya;Coal gas supply road and the one end for vacuumizing road It is connected to adsorption tower group bottom, the one end on purified gas buffering road and the road Jun Ya is connected to adsorption tower group top;Gas-liquid separation The gas vent of device is connected to the other end on coal gas supply road, and liquid outlet is connected to liquid withdrawal system;Vacuum pump and pumping are true The other end of dead circuit is connected to;The entrance of purified gas surge tank is connected to the other end on purified gas buffering road, outlet and MDEA solution Adsorb the connection of fine decarbonization device;Equalizer tank is connected to the other end on the road Jun Ya.
Further, the decarbonization device of coke-stove gas and converter and/or blast furnace gas includes coke oven gas filter, coke oven Coal gas tower top filter, rich solution filter, coke-stove gas absorption tower, regenerator, coke-stove gas cooler, poor rich liquid heat exchanger, Regeneration overhead cooler, reboiler, lean solution cooler, coke-stove gas separator, flash tank, lean solution surge tank, regeneration overhead gas Liquid/gas separator, coke-stove gas lean pump, recovery pump, converter and/or blast furnace gas filter, converter and/or blast furnace gas tower top Filter, converter and/or blast furnace gas absorption tower, converter and/or blast furnace gas cooler, converter and/or blast furnace gas separation Device and converter and/or blast furnace gas lean pump;
Lean solution surge tank is provided with the outlet of the first MDEA lean solution and the outlet of the 2nd MDEA lean solution;
The outlet of first MDEA lean solution is successively connected to the top entry of coke-stove gas lean pump and coke-stove gas absorption tower;It is burnt The outlet of producer gas filter is connected to the bottom inlet on coke-stove gas absorption tower;Gas vent at the top of coke-stove gas absorption tower It is successively connected to the gas access of coke-stove gas cooler and coke-stove gas separator, the liquid discharge of coke-stove gas absorb the bottom of the tower Mouth is connected to flash tank entrance, and the gas vent of coke-stove gas separator is connected to the entrance of coke-stove gas tower top filter, burnt The gas vent of producer gas tower top filter is in communication with the outside, coke-stove gas tower top filter impurity outlet and coke-stove gas point Liquid inlet connection from device, the liquid outlet of coke-stove gas separator are connected to the entrance of flash tank;
The outlet of 2nd MDEA lean solution is successively absorbed with converter and/or blast furnace gas lean pump and converter and/or blast furnace gas The top entry of tower is connected to;The bottom of converter and/or the outlet of blast furnace gas filter and converter and/or blast furnace gas absorption tower Entrance connection;Gas vent at the top of converter and/or blast furnace gas absorption tower successively with converter and/or blast furnace gas cooler and The connection of the gas access of converter and/or blast furnace gas separator, the liquid outlet of converter and/or blast furnace gas absorb the bottom of the tower with The gas vent and converter and/or blast furnace gas tower top filter of the connection of flash tank entrance, converter and/or blast furnace gas separator Entrance connection, the gas vent of converter and/or blast furnace gas tower top filter is in communication with the outside, converter and/or blast furnace gas Tower top filter impurity outlet is connected to the liquid inlet of converter and/or blast furnace gas separator, converter and/or blast furnace gas The liquid outlet of separator is connected to the entrance of flash tank;
Flash tank top gas outlet be in communication with the outside, the liquid outlet of flash tank bottom successively with rich solution filter, Poor rich liquid heat exchanger is connected to the liquid inlet at the top of regenerator;The steam inlet of reboiler is connected to extraneous steam gas source, then The steam (vapor) outlet for boiling device is connected to the steam inlet of regeneration tower bottom, and the gas vent at the top of regenerator is successively cold with regeneration overhead But device is connected to regeneration overhead gas-liquid separator entrance, and the gas vent of regeneration overhead gas-liquid separator is in communication with the outside, regeneration The liquid outlet of tower top gas-liquid separator is successively connected to the entrance of recovery pump and flash tank;Regenerate tower bottom liquid outlet with The liquid inlet of reboiler is connected to, and the taphole of reboiler is successively buffered with poor rich liquid heat exchanger, lean solution cooler and lean solution First MDEA lean solution entrance of tank is connected to.
Further, coke-stove gas deoxygenation fine de-sulfur device, the First Heat Exchanger including passing sequentially through pipeline connection, pre-add Hydrogen reaction unit, level-one hydrogenator, first grade desulfurizing reaction unit, the second heat exchanger, secondary hydrogenation reactor, second level essence are de- Reaction of Salmon-Saxl device and third heat exchanger;Pre-hydrotreating reaction device includes the identical pre-hydrogenator I of structure and pre-add in parallel Hydrogen reactor II;First grade desulfurizing reaction unit includes the identical first grade desulfurizing reactor I of structure in parallel, first grade desulfurizing reactor II and first grade desulfurizing reactor III;Second level fine de-sulfur reaction unit includes identical I He of two-grade desulfurizing reactor of structure in parallel Two-grade desulfurizing reactor II;Pre-hydrogenator I, pre-hydrogenator II, level-one hydrogenator and secondary hydrogenation reactor Structure is identical;First grade desulfurizing reactor I, first grade desulfurizing reactor II, first grade desulfurizing reactor III, I He of two-grade desulfurizing reactor II structure of two-grade desulfurizing reactor is identical.
Further, coke-stove gas deoxygenation fine de-sulfur device includes bye-pass, bye-pass both ends respectively be connected to level-one and add Hydrogen reactor and the pipeline of first grade desulfurizing reaction unit and it is connected to secondary hydrogenation reactor and second level fine de-sulfur reaction unit Pipeline connection.
Further, pre-hydrogenator I includes hydrogenator shell, hydrogenator gas access, hydrogenation reaction Catalyst discharge port under device gas vent, hydrogenator, catalyst discharge port on hydrogenator, under hydrogenator plus hydrogen Oxidant layer, on hydrogenator plus hydrogen oxidant layer, the first screen of hydrogenator, the second screen of hydrogenator, hydrogenator the One silk screen layer, the second silk screen layer of hydrogenator, hydrogenator third silk screen layer, the 4th silk screen layer of hydrogenator add hydrogen Reactor the first porcelain ball transition zone, hydrogenator the second porcelain ball transition zone, hydrogenator third porcelain ball transition zone add hydrogen anti- Answer the 4th porcelain ball transition zone of device, the 5th porcelain ball transition zone of hydrogenator, the 6th porcelain ball transition zone of hydrogenator, hydrogenation reaction The 7th porcelain ball transition zone of device, the 8th porcelain ball transition zone of hydrogenator, manhole in hydrogenator lower manhole and hydrogenator, Hydrogenator shell includes the upper cover being fixedly connected sequentially, cylinder-shaped body and lower head;Hydrogenator gas access Lower head outer surface is set and is connected to the inner cavity of lower head, hydrogenator gas vent setting upper cover outer surface simultaneously It is connected to the inner cavity of upper cover, in cylinder-shaped body, from bottom to top, being fixedly connected sequentially has the first screen of hydrogenator, The first silk screen layer of hydrogenator, the second silk screen layer of hydrogenator, the second screen of hydrogenator, hydrogenator third silk The 4th silk screen layer of stratum reticulare and hydrogenator;Hydrogenator the first porcelain ball transition zone and hydrogenator the second porcelain ball transition zone It sets gradually from bottom to top, hydrogenator the first porcelain ball transition zone is arranged on the first silk screen layer of hydrogenator, adds hydrogen anti- It answers under device plus hydrogen oxidant layer is arranged between the second silk screen layer of hydrogenator the second porcelain ball transition zone and hydrogenator;Add hydrogen anti- Device third porcelain ball transition zone and the 4th porcelain ball transition zone of hydrogenator is answered to set gradually from bottom to top, hydrogenator third porcelain Ball transition zone is arranged on the second silk screen layer of hydrogenator;The 5th porcelain ball transition zone of hydrogenator and hydrogenator the 6th Porcelain ball transition zone is set gradually from bottom to top, and the 5th porcelain ball transition zone of hydrogenator is arranged in hydrogenator third silk screen layer On, on hydrogenator plus the setting of hydrogen oxidant layer the 6th porcelain ball transition zone of hydrogenator and the 4th silk screen layer of hydrogenator it Between;The 7th porcelain ball transition zone of hydrogenator and the 8th porcelain ball transition zone of hydrogenator are set gradually from bottom to top, add hydrogen anti- The 7th porcelain ball transition zone of device is answered to be arranged on the 4th silk screen layer of hydrogenator;Catalyst discharge port and cylinder under hydrogenator Shape body outer surface is fixedly connected and adds hydrogen oxidant layer to be connected to under hydrogenator;Catalyst discharge port and circle on hydrogenator Cylindrical bodies outer surface is fixedly connected and adds hydrogen oxidant layer to be connected to on hydrogenator;Hydrogenator lower manhole and cylinder master External surface be fixedly connected and with the 4th porcelain ball transition zone of hydrogenator and the second screen of hydrogenator in cylinder-shaped body Between space connection;On hydrogenator manhole be fixedly connected with cylinder-shaped body outer surface and in cylinder-shaped body plus hydrogen Space connection between the 8th porcelain ball transition zone of reactor and upper cover.
Further, first grade desulfurizing reactor I is anti-including desulfurization reactor shell, desulfurization reactor gas access, desulfurization Catalyst discharge port under device gas vent, desulfurization reactor, catalyst discharge port on desulfurization reactor are answered, is added under desulfurization reactor Hydrogen oxidant layer, on desulfurization reactor plus hydrogen oxidant layer, the first screen of desulfurization reactor, the second screen of desulfurization reactor, desulfurization reactor First silk screen layer, the second silk screen layer of desulfurization reactor, desulfurization reactor third silk screen layer, the 4th silk screen layer of desulfurization reactor take off Reaction of Salmon-Saxl device the first porcelain ball transition zone, desulfurization reactor the second porcelain ball transition zone, desulfurization reactor third porcelain ball transition zone, desulfurization The 4th porcelain ball transition zone of reactor, the 5th porcelain ball transition zone of desulfurization reactor, the 6th porcelain ball transition zone of desulfurization reactor, desulfurization are anti- Answer the 7th porcelain ball transition zone of device, the 8th porcelain ball transition zone of desulfurization reactor, people in desulfurization reactor lower manhole and desulfurization reactor Hole, desulfurization reactor shell include the upper cover being fixedly connected sequentially, cylinder-shaped body and lower head;Desulfurization reactor gas enters Mouth is arranged in lower head outer surface and is connected to the inner cavity of lower head, and desulfurization reactor gas vent is arranged in upper cover outer surface And be connected to the inner cavity of upper cover, in cylinder-shaped body, from bottom to top, being fixedly connected sequentially has the desulfurization reactor first grid Plate, the first silk screen layer of desulfurization reactor, the second silk screen layer of desulfurization reactor, the second screen of desulfurization reactor, desulfurization reactor The 4th silk screen layer of three silk screen layers and desulfurization reactor;Desulfurization reactor the first porcelain ball transition zone and desulfurization reactor the second porcelain ball mistake It crosses layer to set gradually from bottom to top, desulfurization reactor the first porcelain ball transition zone is arranged on the first silk screen layer of desulfurization reactor, takes off Under reaction of Salmon-Saxl device plus hydrogen oxidant layer is arranged between the second silk screen layer of desulfurization reactor the second porcelain ball transition zone and desulfurization reactor;It is de- Reaction of Salmon-Saxl device third porcelain ball transition zone and the 4th porcelain ball transition zone of desulfurization reactor are set gradually from bottom to top, desulfurization reactor Three porcelain ball transition zones are arranged on the second silk screen layer of desulfurization reactor;The 5th porcelain ball transition zone of desulfurization reactor and desulfurization reactor 6th porcelain ball transition zone is set gradually from bottom to top, and the 5th porcelain ball transition zone of desulfurization reactor is arranged in desulfurization reactor third silk On stratum reticulare, on desulfurization reactor plus hydrogen oxidant layer is arranged in the 6th porcelain ball transition zone of desulfurization reactor and the 4th silk screen of desulfurization reactor Between layer;The 7th porcelain ball transition zone of desulfurization reactor and the 8th porcelain ball transition zone of desulfurization reactor are set gradually from bottom to top, are taken off The 7th porcelain ball transition zone of reaction of Salmon-Saxl device is arranged on the 4th silk screen layer of desulfurization reactor;Under desulfurization reactor catalyst discharge port with Cylinder-shaped body outer surface is fixedly connected and adds hydrogen oxidant layer to be connected to under desulfurization reactor;Catalyst discharge port on desulfurization reactor It is fixedly connected with cylinder-shaped body outer surface and adds hydrogen oxidant layer to be connected to on desulfurization reactor;Desulfurization reactor lower manhole and cylinder Shape body outer surface be fixedly connected and with the 4th porcelain ball transition zone of desulfurization reactor and desulfurization reactor second in cylinder-shaped body Space connection between screen;On desulfurization reactor manhole be fixedly connected with cylinder-shaped body outer surface and in cylinder-shaped body Space connection between the 8th porcelain ball transition zone of desulfurization reactor and upper cover.
Further, converter and/or blast furnace gas deoxygenation fine de-sulfur device, including hydrolysis desulfurizing tower, deoxidation reactor and Fine de-sulfur tower;The entrance of hydrolysis desulfurizing tower is connected to converter and/or blast furnace gas gas holder, and outlet and the entrance of deoxidation reactor connect Logical, two branches of deoxidation reactor outlet setting a, branch exports and deoxidation reactor entrance with hydrolysis desulfurizing tower is connected to Pipeline connection, another branch are connected to the entrance of fine de-sulfur tower.
Further, converter and/or blast furnace gas deoxygenation fine de-sulfur device include coal gas of converter heat exchanger, purified gas water cooling Device, goes into operation heater and hydrolysis desulfurization goes into operation heater;Entrance and the converter of hydrolysis desulfurizing tower is arranged in coal gas of converter heat exchanger And/or between blast furnace gas gas holder, while the setting of coal gas of converter heat exchanger enters in the outlet of connection deoxidation reactor with fine de-sulfur tower The branch road of mouth, purified gas water cooler are arranged on the branch road between coal gas of converter heat exchanger and fine de-sulfur tower;Connection hydrolysis is de- It is provided with the branch that goes into operation on the pipeline of the entrance of sulphur tower and converter and/or blast furnace gas gas holder, the heater that goes into operation setting is going into operation Branch road is provided with hydrolysis desulfurization in connection hydrolysis desulfurizing tower outlet and the pipeline of deoxidation reactor entrance and goes into operation branch, hydrolysis Desulfurization go into operation heater setting hydrolysis desulfurization go into operation on branch road;The outlet of connection deoxidation reactor is exported with hydrolysis desulfurizing tower is connected to With the branch road of deoxidation reactor entrance pipe, connection hydrolysis desulfurizing tower outlet and deoxidation reactor are exported to from deoxidation reactor On the pipeline direction of entrance, it is disposed with circulating air water cooler, circulating air liquid separation tank and converter and/or blast furnace gas circulation pressure Contracting machine.
Further, deoxidation reactor includes shell, upper cover, lower head, several heat exchanger tubes, atmolysis cylinder, manhole pipe orifice, Catalyst self-unloading mouth, air inlet, gas outlet and relief valve;Shell and upper cover and lower head connect and compose pressure shell;It is several Heat exchanger tube is set in shell and is fixedly connected with atmolysis cylinder, and atmolysis cylinder is fixedly connected in lower head, air inlet, gas outlet and Catalyst self-unloading mouth is respectively fixedly connected in lower head outer surface, and air inlet is connected to atmolysis cylinder entrance, if atmolysis cylinder outlet with The connection of dry heat exchanger tube, gas outlet and catalyst self-unloading mouth are connected to lower head inside, manhole pipe orifice and relief valve respectively with upper envelope Head outer surface is fixedly connected and is connected to upper cover inside.
The utility model compared with prior art the advantages of be:
1, the device of the coke-stove gas of the utility model and converter and/or blast furnace gas synthesizing glycol coproduction LNG, sufficiently Using the tail gas generated in coking and steelmaking process, lack H using blast furnace gas, the more CO of coal gas of converter2With oven gas more CH4, H2It is few The characteristics of CO, rationally purification and proportion, make effective gas (CO, H in gas2、CH4) 100% utilization, the efficient of resource may be implemented It makes full use of, reduces the wasting of resources and the pollution to environment, be that steel and Chemical Engineering unit combine the high-quality high-end fine chemistry industry of output Product opens up the beginning.
2, burnt in the device of the coke-stove gas of the utility model and converter and/or blast furnace gas synthesizing glycol coproduction LNG The decarbonization method of producer gas and converter and/or blast furnace gas, compared to other decarburization techniques, improve solution expense reaction rate and Absorptive capacity reduces the regeneration energy consumption of solution, has many advantages, such as that absorption rate is fast, absorbability is big and degree of purification is high, not only It can be used for carbon dioxide removal, it can also be used to sulfide is removed, therefore is had a wide range of applications and development prospect, meanwhile, to pushing away The technological progress and economic development of dynamic China's refinery industry have a very important significance.
3, in the device of the coke-stove gas of the utility model and converter and/or blast furnace gas synthesizing glycol coproduction LNG, wound The property made completes converter and/or the decarburization of blast furnace gas by the thick decarburization of pressure-variable adsorption and two step process of MDEA solution fine decarbonization, The breakthrough for realizing converter and/or blast furnace gas decarburization has the technological progress and economic development that push China's steel industry Highly important meaning.
4, in the device of the coke-stove gas of the utility model and converter and/or blast furnace gas synthesizing glycol coproduction LNG, lead to The thick decarburization of pressure-variable adsorption is crossed by the near 5.8-6.2% of the content of carbon dioxide in converter and/or blast furnace gas, especially 6%, if The content of carbon dioxide is more than above range in converter and/or blast furnace gas after thick decarburization, then subsequent use will be significantly increased MDEA solution cannot achieve industrialization, such as so that decarburization cost greatly improves to the load of converter and/or blast furnace gas decarburization The content of carbon dioxide is lower than above range in converter and/or blast furnace gas after the thick decarburization of fruit, then cannot achieve MDEA solution Efficient Cycle, cause subsequent using MDEA solution is to converter and/or blast furnace gas decarburization can not start or fallback.
5, burnt in the device of the coke-stove gas of the utility model and converter and/or blast furnace gas synthesizing glycol coproduction LNG The method of producer gas deoxygenation fine de-sulfur, using two-stage coke-stove gas deoxidization by adding hydrogen fine desulfurizing technology, the basic principle is that according to change Thermodynamics of reactions and principle of dynamics are learned, using level-one deoxidization by adding hydrogen desulfurization workshop section by most of organic sulfur in coke-stove gas (such as COS, CS2, CH3SSCH3, methyl mercaptan etc.) is converted to H2S, by most of oxygen hydrogenation and removing, by most of unsaturated hydrocarbons Add hydrogen to be saturated, while other impurity (arsenic, tar, dust, benzene, naphthalene, ammonia, hydrogen cyanide, hydrogen sulfide etc.) being handled;By place The coke-stove gas of reason enters back into secondary hydrogenation deoxygenation fine de-sulfur workshop section, by impurity such as remaining organic sulfur, unsaturated hydrocarbons, micro amount of oxygen Secondary deep hydro-conversion and processing are carried out, realizes coke-stove gas deep purifying.The coke-stove gas deoxygenation essence of the utility model is de- The method of sulphur is simple with process flow, operating condition is mild, operational reliability and safety are good, Load Regulation is convenient, automatic The advantages that change degree is high.Compared with other advanced purification technologies, in each side such as technique, operation, maintenance, economy, Load Regulations There is apparent advantages in face.
6, in the device of the coke-stove gas of the utility model and converter and/or blast furnace gas synthesizing glycol coproduction LNG, turn The deoxygenation fine de-sulfur of furnace and/or blast furnace gas, simple process is easy to operate, using by the higher coal gas of oxygen content and oxygen The low qualified coal gas of content is mixed, and mixed coal gas is then passed through deoxidation reactor and carries out deoxidation treatment, is closed The regeneration gas of lattice, while a part of coal gas being recycled through recycle compressor, it is mixed for the higher coal gas of oxygen content Close, be made gaseous mixture, entire simple process, energy consumption is small, can real-time online continuously to coal gas carry out deoxidation treatment.
Detailed description of the invention
Fig. 1 is the coke-stove gas and the device of converter and/or blast furnace gas synthesizing glycol coproduction LNG of the utility model Schematic diagram.
Fig. 2 is the coke-stove gas and converter and/or blast furnace gas synthesizing glycol coproduction LNG device using the utility model Utilize coke-stove gas and converter and/or the flow chart of blast furnace gas synthesizing glycol coproduction LNG.
Fig. 3 is coke-stove gas and the converter and/or blast furnace gas synthesizing glycol coproduction LNG device transfer of the utility model The schematic diagram of furnace and/or the rough decarbonization device of blast furnace coal.
Fig. 4 is burnt in the coke-stove gas and converter and/or blast furnace gas synthesizing glycol coproduction LNG device of the utility model The flow chart of producer gas deoxygenation desulfurizing process.
Fig. 5 is the coke-stove gas and converter and/or blast furnace gas synthesizing glycol coproduction LNG method for realizing the utility model The schematic diagram of the coke-stove gas deoxygenation fine de-sulfur device of middle coke-stove gas deoxygenation desulfurizing process.
Fig. 6 is the structural schematic diagram of pre-hydrogenator I in coke-stove gas deoxygenation fine de-sulfur device in Fig. 5.
Fig. 7 is the structural schematic diagram of first grade desulfurizing reactor I in coke-stove gas deoxygenation fine de-sulfur device in Fig. 5.
Fig. 8 is furnace in the coke-stove gas and converter and/or blast furnace gas synthesizing glycol coproduction LNG method of the utility model And/or the flow chart of blast furnace gas deoxygenation desulfurizing process.
Fig. 9 is the coke-stove gas and converter and/or blast furnace gas synthesizing glycol coproduction LNG method for realizing the utility model The schematic diagram of middle converter and/or the converter of blast furnace gas deoxygenation desulfurizing process and/or blast furnace gas deoxygenation fine de-sulfur device.
Figure 10 is the structural schematic diagram of deoxidation reactor in converter and/or blast furnace gas deoxygenation fine de-sulfur device in Fig. 9.
Specific embodiment
In the description of the present invention, it should be understood that term " center ", " longitudinal direction ", " transverse direction ", " length ", " width Degree ", " thickness ", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom" "inner", "outside", " suitable The orientation or positional relationship of the instructions such as hour hands ", " counterclockwise ", " axial direction ", " radial direction ", " circumferential direction " is orientation based on the figure Or positional relationship, be merely for convenience of describing the present invention and simplifying the description, rather than the device of indication or suggestion meaning or Element must have a particular orientation, be constructed and operated in a specific orientation, therefore should not be understood as the limit to the utility model System.In addition, defining " first ", the feature of " second " can explicitly or implicitly include one or more of the features. In the description of the present invention, unless otherwise indicated, the meaning of " plurality " is two or more.
In the description of the present invention, it should be noted that unless otherwise clearly defined and limited, term " is pacified Dress ", " connected ", " connection " shall be understood in a broad sense, for example, it may be being fixedly connected, may be a detachable connection, or integrally Connection;It can be mechanical connection, be also possible to be electrically connected;Can be directly connected, can also indirectly connected through an intermediary, It can be the connection inside two elements.For the ordinary skill in the art, above-mentioned art can be understood with concrete condition The concrete meaning of language in the present invention.
As Figure 1-10 shows, the method for a kind of coke-stove gas and converter and/or blast furnace gas synthesizing glycol coproduction LNG, The coke gas flow is 80000-85000Nm3/ h, pressure 0.004-0.006Mpa, temperature are 18-22 DEG C;Effectively at In point, the volume fraction of methane is 20-25%, and the volume fraction of hydrogen is 60-65%, and the volume fraction of carbon monoxide is 8- 12%, the volume fraction 0.5-0.9% of oxygen, the volume fraction of carbon dioxide are 2-4%, and the content of tar and dust is 0.14- 0.16g/Nm3, the content of hydrogen sulfide is 50-150mg/Nm3, the content of other sulfide is 150-160mg/Nm3.Converter and/or The flow of blast furnace gas is 28000-30000Nm3/ h, pressure 0.003-0.005Mpa, temperature are 18-22 DEG C;Effective component In, the volume fraction of carbon monoxide is 40-60%, and the volume fraction of carbon dioxide is 20-26%, and the volume fraction of nitrogen is 20-28%, the volume fraction of hydrogen are 1-4%, and the volume fraction of oxygen is 0.6-1%;The content of hydrogen phosphide is 100- The content of 250mg/kg, tar and dust is 0.01-0.02g/Nm3, the content of sulfide is 16-18mg/Nm3
Include the following steps:
S0), coke-stove gas and converter and/or blast furnace gas just purify
Purification device at the beginning of using coke-stove gas just purifies coke-stove gas by coke-stove gas, and the coke-stove gas just purifies Device includes sequentially connected dedusting detar device, compressor, desulfurizer, TSA adsorbent equipment and compressor;Preferably, The dedusting detar device is electrical tar precipitator, and the compressor between dedusting detar device and desulfurizer is screw compression Machine, desulfurizer are the compression using iron oxide as the desulfurizer of desulfurizing agent, between TSA adsorbent equipment and deoxygenation fine de-sulfur device Machine is centrifugal compressor.
Coke-stove gas, which just purifies, to be included the following steps:
S01), dedusting detar: using dedusting detar device, preferably electrical tar precipitator to the coke-stove gas dedusting and Detar makes dust and tar total amount in the coke-stove gas be not higher than 3mg/Nm3
S02), compress: using compressor, preferably helical-lobe compressor compression is by the coke-stove gas of step S01 to 0.58- 0.62Mpa, because still having tar in coke-stove gas by step S01, using other kinds of compressor, in coke-stove gas Tar will cause the damage of compressor, and use helical-lobe compressor can be to avoid the generation of above situation.
S03), thick desulfurization: desulfurizer is used, is preferably the desulfurizer of desulfurizing agent to by step S02 using iron oxide The rough desulfurization of coke-oven coal, make the H in coke-stove gas2S content is not higher than 1mg/Nm3
S04), clean: being cleaned, made miscellaneous in coke-stove gas to by the coke-stove gas of step S03 using TSA adsorbent equipment Matter content is not higher than 0.1mg/Nm3;The impurity is arsenic, tar, dust, naphthalene, benzene, one of hydrogen cyanide and ammonia or a variety of groups It closes.
S05), second-compressed: compressor is used, preferably centrifugal compressor compression is by the coke-stove gas of step S04 to 4- 4.2Mpa, preferably 4Mpa are to improve subsequent handling, for example when subsequent handling includes deoxygenation fine de-sulfur, when cryogenic separation, improve burnt The pressure of producer gas helps to improve the effect and efficiency of deoxygenation fine de-sulfur and cryogenic separation.
S06), deoxygenation fine de-sulfur: using coke-stove gas deoxygenation fine de-sulfur device to the coke-stove gas deoxygenation by step S05 Fine de-sulfur makes the total sulfur content in coke-stove gas not higher than 0.1PPM, and oxygen content is not higher than 1PPM.
Wherein, the coke-stove gas deoxygenation fine de-sulfur device includes the First Heat Exchanger 610 for passing sequentially through pipeline connection, in advance Hydrogenation reaction device 100, level-one hydrogenator 200, first grade desulfurizing reaction unit 300, the second heat exchanger 620, secondary hydrogenation Reactor 400, second level fine de-sulfur reaction unit 500, third heat exchanger 630 and bye-pass 700;The pre-hydrotreating reaction device 100 include the identical pre-hydrogenator I 110 of structure and pre-hydrogenator II 120 in parallel;The first grade desulfurizing reaction dress Setting 300 includes the identical first grade desulfurizing reactor I 310 of structure in parallel, first grade desulfurizing reactor II 320 and first grade desulfurizing reaction Device III 330;The second level fine de-sulfur reaction unit 500 includes the identical two-grade desulfurizing reactor I 510 of structure and second level in parallel Desulfurization reactor II 520;The pre-hydrogenator I 110, pre-hydrogenator II 120, level-one hydrogenator 200 and two Grade 400 structure of hydrogenator is identical;The first grade desulfurizing reactor I 310, first grade desulfurizing reactor II 320, first grade desulfurizing is anti- Device III 330 is answered, two-grade desulfurizing reactor I 510 is identical with II 520 structure of two-grade desulfurizing reactor, 700 both ends of bye-pass point Not with the pipeline that is connected to level-one hydrogenator 200 and first grade desulfurizing reaction unit 300 and connection secondary hydrogenation reactor 400 It is realized by the way that bye-pass 700 is arranged by a part of level-one hydro-conversion with the pipeline connection of second level fine de-sulfur reaction unit 500 Coke-stove gas afterwards is by the coke-stove gas before the introducing secondary hydrogenation of bye-pass 700 and mixing, before control carries out secondary hydrogenation The total sulfur of coke-stove gas is 10-15mg/m3, to maintain the dynamic sulfur balance of secondary hydrogenation catalyst, guarantee that it efficiently adds hydrogen Activity of conversion.
Preferably, the pre-hydrogenator I 110 includes hydrogenator shell 101, hydrogenator gas access 102, catalyst discharge port 104-1 under hydrogenator gas vent 103, hydrogenator, catalyst unloads on hydrogenator Material mouth 104-2, under hydrogenator plus hydrogen oxidant layer 105-1, on hydrogenator plus hydrogen oxidant layer 105-2, hydrogenator first Screen 106-1, hydrogenator the second screen 106-2, hydrogenator the first silk screen layer 107-1, hydrogenator second Stratum reticulare 107-2, hydrogenator third silk screen layer 107-3, the 4th silk screen layer 107-4 of hydrogenator, hydrogenator first Porcelain ball transition zone 108-1, hydrogenator the second porcelain ball transition zone 108-2, hydrogenator third porcelain ball transition zone 108-3, The 4th porcelain ball transition zone 108-4 of hydrogenator, the 5th porcelain ball transition zone 108-5 of hydrogenator, the 6th porcelain of hydrogenator Ball transition zone 108-6, the 7th porcelain ball transition zone 108-7 of hydrogenator, the 8th porcelain ball transition zone 108-8 of hydrogenator add Manhole 109-2 on hydrogen reactor lower manhole 109-1 and hydrogenator.The hydrogenator shell 101 includes successively fixing The upper cover of connection, cylinder-shaped body and lower head;The hydrogenator gas access 102 is arranged in the lower head appearance Face is simultaneously connected to the inner cavity of the lower head, the hydrogenator gas vent 103 setting the upper cover outer surface simultaneously It is connected to the inner cavity of the upper cover, in the cylinder-shaped body, from bottom to top, being fixedly connected sequentially has hydrogenator One screen 106-1, hydrogenator the first silk screen layer 107-1, hydrogenator the second silk screen layer 107-2, hydrogenator The 4th silk screen layer 107-4 of two screen 106-2, hydrogenator third silk screen layer 107-3 and hydrogenator;The hydrogenation reaction The first porcelain of device ball transition zone 108-1 and hydrogenator the second porcelain ball transition zone 108-2 are set gradually from bottom to top, described plus hydrogen The first porcelain of reactor ball transition zone 108-1 is arranged on the first silk screen layer of hydrogenator 107-1, the hydrogenator Down plus hydrogen oxidant layer 105-1 is arranged in the second porcelain of hydrogenator ball transition zone 108-2 and the second silk screen layer of hydrogenator 107-2 Between;The hydrogenator third porcelain ball transition zone 108-3 and the 4th porcelain ball transition zone 108-4 of hydrogenator are from bottom to top It sets gradually, the hydrogenator third porcelain ball transition zone 108-3 is arranged in the second silk screen layer of hydrogenator 107-2 On;The 5th porcelain ball transition zone 108-5 of hydrogenator and the 6th porcelain ball transition zone 108-6 of hydrogenator from bottom to top according to Secondary setting, the 5th porcelain ball transition zone 108-5 of hydrogenator are arranged in the hydrogenator third silk screen layer 107-3 On, on the hydrogenator plus hydrogen oxidant layer 105-2 is arranged in the 6th porcelain ball transition zone 108-6 of hydrogenator and hydrogenation reaction Between the 4th silk screen layer 107-4 of device;The 7th porcelain ball transition zone 108-7 of hydrogenator and the 8th porcelain ball mistake of hydrogenator It crosses a layer 108-8 to set gradually from bottom to top, the 7th porcelain ball transition zone 108-7 of hydrogenator is arranged in the hydrogenation reaction On the 4th silk screen layer 107-4 of device;Catalyst discharge port 104-1 and the cylinder-shaped body outer surface are solid under the hydrogenator It is fixed to connect and add hydrogen oxidant layer 105-1 to be connected to under the hydrogenator;Catalyst discharge port 104-2 on the hydrogenator It is fixedly connected with the cylinder-shaped body outer surface and adds hydrogen oxidant layer 105-2 to be connected to on the hydrogenator;Add hydrogen agent point It Tong Guo not catalyst discharge port 104-2 handling on catalyst discharge port 104-1 and hydrogenator under hydrogenator;It is described to add Hydrogen reactor lower manhole 109-1 be fixedly connected with the cylinder-shaped body outer surface and with hydrogenator in cylinder-shaped body Space connection between four porcelain ball transition zone 108-4 and the second screen of hydrogenator 106-2;Manhole on the hydrogenator 109-2 be fixedly connected with the cylinder-shaped body outer surface and with the 8th porcelain ball transition zone of hydrogenator in cylinder-shaped body Space connection between 108-8 and upper cover, porcelain ball pass through people on hydrogenator lower manhole 109-1 and hydrogenator respectively Hole 109-2 handling.It will cause gas in reactor when one kind plus hydrogen agent bed are excessively high to be unevenly distributed, and be divided into multiple beds Afterwards, by the adjusting of screen and silk screen, further gas can be made to be uniformly distributed, so that the utilization rate that reactor adds hydrogen agent is improved, Extend the service life for adding hydrogen agent.Therefore, the hydrogenator of the application adds hydrogen oxidant layer to can be set to multilayer, here, it is preferred that Two layers.
Preferably, the first silk screen layer of hydrogenator 107-1, hydrogenator the second silk screen layer 107-2, adds hydrogen anti- Device third silk screen layer 107-3 is answered, the 4th silk screen layer 107-4 of hydrogenator is two layers of silk screen, and two layers of silk screen is on the one hand Play the role of supporting hydrogenator porcelain ball transition zone, on the other hand realizes even gas distribution.
The working principle of the hydrogenator is that gas enters from the gas access of reactor bottom 102, is passed sequentially through Hydrogenator the first screen 106-1, the first silk screen layer of hydrogenator 107-1, the first porcelain ball transition zone 108-1 and plus hydrogen it is anti- It answers after device the second porcelain ball transition zone 108-2 even under hydrogenator plus hydrogen oxidant layer 105-1, under hydrogenator plus hydrogen Oxidant layer 105-1, gas with plus hydrogen agent occur physical-chemical reaction after, successively pass through the second silk screen layer of hydrogenator 107-2, add Hydrogen reactor third porcelain ball transition zone 108-3, the 4th porcelain ball transition zone 108-4 of hydrogenator, the second screen of hydrogenator 106-2, hydrogenator third silk screen layer 107-3, the 5th porcelain ball transition zone 108-5 of hydrogenator and hydrogenator the 6th More uniform the entering on hydrogenator of porcelain ball transition zone 108-6 adds hydrogen oxidant layer 105-2 and adds hydrogen agent generation physical chemistry anti- Answer, the gas after reaction pass through the 4th silk screen layer 107-4 of hydrogenator, the 7th porcelain ball transition zone 108-7 of hydrogenator and The 8th porcelain ball transition zone 108-8 of hydrogenator is discharged by hydrogenator gas vent 103.
Preferably, the first grade desulfurizing reactor I 310 includes desulfurization reactor shell 301, desulfurization reactor gas access 302, catalyst discharge port 304-1 under desulfurization reactor gas vent 303, desulfurization reactor, catalyst unloads on desulfurization reactor Material mouth 304-2, desulfurization oxidant layer 305-1 under desulfurization reactor, desulfurization oxidant layer 305-2 on desulfurization reactor, desulfurization reactor first Screen 306-1, desulfurization reactor the second screen 306-2, desulfurization reactor the first silk screen layer 307-1, desulfurization reactor second Stratum reticulare 307-2, desulfurization reactor third silk screen layer 307-3, the 4th silk screen layer 307-4 of desulfurization reactor, desulfurization reactor first Porcelain ball transition zone 308-1, desulfurization reactor the second porcelain ball transition zone 308-2, desulfurization reactor third porcelain ball transition zone 308-3, The 4th porcelain ball transition zone 308-4 of desulfurization reactor, the 5th porcelain ball transition zone 308-5 of desulfurization reactor, the 6th porcelain of desulfurization reactor Ball transition zone 308-6, the 7th porcelain ball transition zone 308-7 of desulfurization reactor, the 8th porcelain ball transition zone 308-8 of desulfurization reactor take off Manhole 309-2 on reaction of Salmon-Saxl device lower manhole 309-1 and desulfurization reactor.The desulfurization reactor shell 301 includes successively fixing The upper cover of connection, cylinder-shaped body and lower head;The desulfurization reactor gas access 302 is arranged in the lower head appearance Face is simultaneously connected to the inner cavity of the lower head, the desulfurization reactor gas vent 303 setting the upper cover outer surface simultaneously It is connected to the inner cavity of the upper cover, in the cylinder-shaped body, from bottom to top, being fixedly connected sequentially has desulfurization reactor One screen 306-1, desulfurization reactor the first silk screen layer 307-1, desulfurization reactor the second silk screen layer 307-2, desulfurization reactor The 4th silk screen layer 307-4 of two screen 306-2, desulfurization reactor third silk screen layer 307-3 and desulfurization reactor;The desulphurization reaction The first porcelain of device ball transition zone 308-1 and desulfurization reactor the second porcelain ball transition zone 308-2 are set gradually from bottom to top, the desulfurization The first porcelain of reactor ball transition zone 308-1 is arranged on the first silk screen layer of desulfurization reactor 307-1, the desulfurization reactor Lower desulfurization oxidant layer 305-1 is arranged in the second porcelain of desulfurization reactor ball transition zone 308-2 and the second silk screen layer of desulfurization reactor 307-2 Between;The desulfurization reactor third porcelain ball transition zone 308-3 and the 4th porcelain ball transition zone 308-4 of desulfurization reactor are from bottom to top It sets gradually, the desulfurization reactor third porcelain ball transition zone 308-3 is arranged in the second silk screen layer of desulfurization reactor 307-2 On;The 5th porcelain ball transition zone 308-5 of desulfurization reactor and the 6th porcelain ball transition zone 308-6 of desulfurization reactor from bottom to top according to Secondary setting, the 5th porcelain ball transition zone 308-5 of desulfurization reactor are arranged in the desulfurization reactor third silk screen layer 307-3 On, desulfurization oxidant layer 305-2 is arranged in the 6th porcelain ball transition zone 308-6 of desulfurization reactor and desulphurization reaction on the desulfurization reactor Between the 4th silk screen layer 307-4 of device;The 7th porcelain ball transition zone 308-7 of desulfurization reactor and the 8th porcelain ball mistake of desulfurization reactor It crosses a layer 308-8 to set gradually from bottom to top, the 7th porcelain ball transition zone 308-7 of desulfurization reactor is arranged in the desulphurization reaction On the 4th silk screen layer 307-4 of device;Catalyst discharge port 304-1 and the cylinder-shaped body outer surface are solid under the desulfurization reactor It is fixed to connect and be connected to desulfurization oxidant layer 305-1 under the desulfurization reactor;Catalyst discharge port 304-2 on the desulfurization reactor It is fixedly connected with the cylinder-shaped body outer surface and is connected to desulfurization oxidant layer 305-2 on the desulfurization reactor;Desulfurizing agent point It Tong Guo not catalyst discharge port 304-2 handling on catalyst discharge port 304-1 and desulfurization reactor under desulfurization reactor;It is described de- Reaction of Salmon-Saxl device lower manhole 309-1 be fixedly connected with the cylinder-shaped body outer surface and with desulfurization reactor in cylinder-shaped body Space connection between four porcelain ball transition zone 308-4 and the second screen of desulfurization reactor 306-2;Manhole on the desulfurization reactor 309-2 be fixedly connected with the cylinder-shaped body outer surface and with the 8th porcelain ball transition zone of desulfurization reactor in cylinder-shaped body Space connection between 308-8 and upper cover, porcelain ball pass through people on desulfurization reactor lower manhole 309-1 and desulfurization reactor respectively Hole 309-2 handling.It will cause gas in reactor when a kind of desulfurizing agent bed is excessively high to be unevenly distributed, and be divided into multiple beds Afterwards, by the adjusting of screen and silk screen, further gas can be made to be uniformly distributed, so that the utilization rate of reactor desulfurizing agent is improved, Extend the service life of desulfurizing agent.Therefore, the desulfurization reactor desulfurization oxidant layer of the application can be set to multilayer, here, it is preferred that Two layers.
Preferably, the first silk screen layer of desulfurization reactor 307-1, desulfurization reactor the second silk screen layer 307-2, desulfurization are anti- Device third silk screen layer 307-3 is answered, the 4th silk screen layer 307-4 of desulfurization reactor is two layers of silk screen, and two layers of silk screen is on the one hand Play the role of supporting desulfurization reactor porcelain ball transition zone, on the other hand realizes even gas distribution.
The working principle of the desulfurization reactor is that gas enters from the gas access of reactor bottom 302, is passed sequentially through Desulfurization reactor the first screen 306-1, the first silk screen layer of desulfurization reactor 307-1, the first porcelain ball transition zone 308-1 and desulfurization are anti- The desulfurization under desulfurization reactor even into desulfurization oxidant layer 305-1 under desulfurization reactor is answered after device the second porcelain ball transition zone 308-2 After physical-chemical reaction occurs for oxidant layer 305-1, gas and desulfurizing agent, successively pass through the second silk screen layer of desulfurization reactor 307-2, takes off Reaction of Salmon-Saxl device third porcelain ball transition zone 308-3, the 4th porcelain ball transition zone 308-4 of desulfurization reactor, the second screen of desulfurization reactor 306-2, desulfurization reactor third silk screen layer 307-3, the 5th porcelain ball transition zone 308-5 of desulfurization reactor and desulfurization reactor the 6th Physical chemistry occurs for desulfurization oxidant layer 305-2 and desulfurizing agent anti-on porcelain ball transition zone 308-6 more uniform entrance desulfurization reactor Answer, the gas after reaction pass through the 4th silk screen layer 307-4 of desulfurization reactor, the 7th porcelain ball transition zone 308-7 of desulfurization reactor and The 8th porcelain ball transition zone 308-8 of desulfurization reactor is discharged by desulfurization reactor gas vent 303.
Preferably, the second porcelain of hydrogenator ball transition zone 108-2, hydrogenator third porcelain ball transition zone 108- 3, the 6th porcelain ball transition zone 108-6 of hydrogenator, the 7th porcelain ball transition zone 108-7 of hydrogenator, desulfurization reactor second Porcelain ball transition zone 308-2, desulfurization reactor third porcelain ball transition zone 308-3, the 6th porcelain ball transition zone 308-6 of desulfurization reactor and The a height of 100mm of layer of the 7th porcelain ball transition zone 308-7 of desulfurization reactor, the diameter of the porcelain ball used is 6mm, the hydrogenation reaction Device the first porcelain ball transition zone 108-1, the 4th porcelain ball transition zone 108-4 of hydrogenator, the 5th porcelain ball transition zone of hydrogenator 108-5, the 8th porcelain ball transition zone 108-8 of hydrogenator, desulfurization reactor the first porcelain ball transition zone 308-1, desulfurization reactor 4th porcelain ball transition zone 308-4, the 5th porcelain ball transition zone 308-5 of desulfurization reactor and the 8th porcelain ball transition zone of desulfurization reactor The a height of 100-200mm of the layer of 308-8, the diameter of the porcelain ball used is 13mm or 25mm;By every layer of contact plus hydrogen agent or catalyst Porcelain ball be set as minor diameter porcelain ball, help to make gas further uniformly distributed, and then improve reaction efficiency and plus hydrogen agent or catalysis The utilization rate of agent.
The method of the deoxygenation fine de-sulfur includes the following steps:
S1), the coke-stove gas heat exchange of compression heat exchange heating: is warming up to 180-300 DEG C using First Heat Exchanger 610;
S2), the coke-stove gas after heat exchange heating pre- hydro-conversion and level-one hydro-conversion: is passed sequentially through into pre-hydrotreating reaction Device 100 and level-one hydrogenator 200 carry out pre- hydro-conversion and level-one hydro-conversion, by the coke-stove gas after heat exchange heating In organic sulfur conversion be hydrogen sulfide, by heat exchange heating after coke-stove gas in oxygen hydrogenation and removing, will heat exchange heating after coke Hydrogenation of unsaturated hydrocarbons saturation in producer gas, the impurity in coke-stove gas after removal heat exchange heating;The organic sulfur be COS, CS2、CH3SSCH3, one of methyl mercaptan or multiple combinations;The impurity is arsenic, in tar, dust, stupid, naphthalene, ammonia, hydrogen cyanide One or more combinations.
S3), first grade desulfurizing: taken off level-one is carried out by first grade desulfurizing reaction unit 300 by the coke-stove gas of step S2 Sulphur removes inorganic sulfur and hydrogen chloride.Preferably, the first grade desulfurizing reaction unit 300 is moderate temperature desulphurization slot, and removing level-one adds hydrogen The inorganic sulfur and hydrogen chloride in coke-stove gas afterwards;The inorganic sulfur is hydrogen sulfide.
S4), secondary heat exchange heats up: will be warming up to 280-340 by the heat exchange of the second heat exchanger 620 by the coke-stove gas of S3 ℃。
S5), secondary hydrogenation converts: will carry out secondary plus hydrogen by secondary hydrogenation reactor 400 by the coke-stove gas of S4 Reaction will be converted by organic sulfur turn, unsaturated hydrocarbons and oxygen deep hydrogenation remaining in the coke-stove gas of S4, i.e., by secondary heat exchange The organic sulfur conversion in coke-stove gas after heating is hydrogen sulfide, and the oxygen in coke-stove gas after secondary heat exchange is heated up adds hydrogen to take off It removes, the hydrogenation of unsaturated hydrocarbons saturation in the coke-stove gas after secondary heat exchange is heated up.
S6), second level fine de-sulfur: coke-stove gas after secondary hydrogenation is converted by second level fine de-sulfur reaction unit 500 into Row second level fine de-sulfur controls the total sulfur in gas and is removed to not higher than 0.1PPM, and is warming up to by third heat exchanger 630 subsequent Process required temperature.
Preferably, before the coke-stove gas after a part of level-one hydro-conversion being introduced secondary hydrogenation by bye-pass 700 Coke-stove gas simultaneously mixes, and the total sulfur that control carries out the coke-stove gas before secondary hydrogenation is 10-15mg/m3, preferably 12mg/m3, with dimension The dynamic sulfur balance for holding secondary hydrogenation catalyst guarantees its efficient hydro-conversion activity.
Purification device at the beginning of using converter and/or blast furnace gas just purifies converter and/or blast furnace gas, the converter and/ Or just purification device includes sequentially connected dedusting detar device to blast furnace gas, compressor, TSA adsorbent equipment and deoxygenation essence are de- Sulphur device;Preferably, the dedusting detar device is electrical tar precipitator, and the compressor is reciprocating compressor, the TSA Adsorbent equipment is alternating temperature carbon adsorption device.
Converter and/or blast furnace gas, which just purify, to be included the following steps:
S01), dedusting detar: dedusting detar device is used, preferably electrical tar precipitator is to the converter and/or blast furnace Coal gas dust removal and detar make dust and tar total amount in the converter and/or blast furnace gas be not higher than 3mg/Nm3
S02), compress: using compressor, preferably converter and/or blast furnace gas of the reciprocating compressor compression by step S01 To 0.95-1Mpa.
S03), clean: using TSA adsorbent equipment, preferably alternating temperature carbon adsorption device, converter and/or blast furnace to step S02 Coal gas removal of impurities makes the impurity content in the converter and/or blast furnace gas not higher than 0.1mg/Nm3.The impurity be tar and/ Or dust.
S04), deoxygenation fine de-sulfur: removed using deoxygenation fine de-sulfur device to by the converter and/or blast furnace gas of step S03 Oxygen fine de-sulfur makes the total sulfur content in the coke-stove gas not higher than 0.1mg/Nm3, the volume fraction of oxygen is 0.001- 0.005%.
The deoxygenation fine de-sulfur device includes coal gas of converter heat exchanger 301, and go into operation heater 302, circulating air water cooler 303, purified gas water cooler 304, hydrolysis desulfurization goes into operation heater 305, hydrolyzes desulfurizing tower, fine de-sulfur tower, deoxidation reactor 350, Converter and/or blast furnace gas recycle compressor 360, circulating air liquid separation tank 370, wherein the hydrolysis desulfurizing tower includes structure phase Same the first hydrolysis desulfurizing tower 310 and the second hydrolysis desulfurizing tower 320, the first hydrolysis desulfurizing tower 310 and the second hydrolysis desulfurization Tower 320 is normally produced as serial flow using that can go here and there and can and be arranged, and when more catalyst changeout using parallel operation, the essence is de- Sulphur tower includes identical first fine de-sulfur tower 330 of structure and the first fine de-sulfur tower 340, first fine de-sulfur tower 330 and first Fine de-sulfur tower 340 is arranged in parallel, and one opens one standby, and tower is provided with desulfurizing agent, removes mercaptan and dimethyl two remaining in gas Sulfide.
Converter and/or blast furnace gas gas holder hydrolyze desulfurizing tower, deoxidation reactor 350 successively with coal gas of converter heat exchanger 301 Connection, the deoxidation reactor 350 include shell 351, upper cover 352-1, lower head 352-2, and several heat exchanger tubes 353 divide gas Cylinder 354, manhole pipe orifice 355, catalyst self-unloading mouth 356, air inlet 357, gas outlet 358 and relief valve 359;The shell 351 Pressure shell is connected and composed with upper cover 352-1 and lower head 352-2;Several heat exchanger tubes 353 are set to the shell 351 Interior and be fixedly connected with the atmolysis cylinder 354, the atmolysis cylinder 354 is fixedly connected in the lower head 352-2, the air inlet Mouth 357, gas outlet 358 and catalyst self-unloading mouth 356 are respectively fixedly connected in the outer surface the lower head 352-2, the air inlet Mouthfuls 357 be connected tos with 354 entrance of atmolysis cylinder, and the atmolysis cylinder 354 is exported and is connected to several heat exchanger tubes 353, it is described out It is connected to inside port 358 and catalyst self-unloading mouth 356 and the lower head 352-2, the manhole pipe orifice 355 and relief valve 359 It is fixedly connected with the outer surface the upper cover 352-1 and is connected to the inside upper cover 352-1 respectively.Deoxidation catalyst is from de- The manhole pipe orifice 355 of the upper cover 352-1 at 350 top of oxygen reactor is packed into, between several heat exchanger tubes 353 and anti-by deoxidation 356 discharging of catalyst self-unloading mouth for answering the lower head 352-2 of 350 bottom of device, it is further preferred that the catalyst self-unloading mouth 356 dischargings are 2, are arranged in the two sides the lower head 352-2.It is further preferred that the operation pressure of the deoxidation reactor 350 Power is 0.95-1.05Mpa, preferably 1Mpa, and operation temperature is 50-160 DEG C, and preferably 56 DEG C, catalyst filling particle diameter is ф 3- 4mm, 351 internal diameter of shell are 3700mm, and 350 whole height of deoxidation reactor is 8000mm.The outlet of deoxidation reactor 350 is set Two branches are set, a branch hydrolyzes the pipeline connection of desulfurizing tower outlet and 350 entrance of deoxidation reactor with being connected to, in the branch On, it is exported in connection hydrolysis desulfurizing tower outlet and the pipeline direction of 350 entrance of deoxidation reactor from deoxidation reactor 350, according to It is secondary to be provided with circulating air water cooler 303, circulating air liquid separation tank 370 and converter and/or blast furnace gas recycle compressor 360;It is another Successively with coal gas of converter heat exchanger 301, purified gas water cooler 304 is connected to the entrance of fine de-sulfur tower for branch;It is connected to the water It solves and is provided with the branch that goes into operation on the entrance and the pipeline of converter and/or blast furnace gas gas holder of desulfurizing tower, the hydrolysis desulfurization goes into operation The setting of heater 305 goes into operation on branch road described, is connected to the pipeline of hydrolysis desulfurizing tower outlet and 350 entrance of deoxidation reactor On be provided with hydrolysis desulfurization and go into operation branch, the setting of heater 302 that goes into operation goes into operation on branch road in the hydrolysis desulfurization.
The deoxygenation fine de-sulfur includes the following steps:
S041), desulfurization: the body of the converter and/or the blast furnace gas oxygen after coal gas of converter heat exchanger 301 and deoxidation Deoxidation coal gas heat exchange of the integration rate no more than 0.7% enters hydrolysis desulfurizing tower removing organic sulfur and inorganic after being warming up to 55-65 DEG C Sulphur, detailed process are converter and/or blast furnace gas by the organic sulfur hydrolyst of hydrolysis desulfurizing tower by converter and/or height COS hydrolysis in producer gas is H2S removes the H in gas subsequently into the desulfurizing agent bed of hydrolysis desulfurizing tower2S and Other sulfide, other sulfide include dimethyl disulfide, one of methyl mercaptan and thiophene or multiple combinations.In converter and/or Desulfurization process is carried out before blast furnace gas deoxidation, is avoided in the sulfide and deoxidation reactor in converter and/or blast furnace gas Deoxidation catalyst reaction is so that deoxidation catalyst fails.Before converter and/or blast furnace gas desulfurization, by converter and/or blast furnace gas Heat exchange heating, improves the desulfurization effect of converter and/or blast furnace gas.
S042), mix: the volume fraction by converter and/or blast furnace gas and oxygen after step S041 desulfurization is The deoxidation circulating gas of 0.001-0.005% mixes, and controls in mixed mixed gas, the volume fraction of oxygen is not more than 0.7%.
S043), the mixed mixed gas deoxidation of step S042, the oxygen of the deoxidation coal gas after making deoxidation deoxidation: will be passed through The volume fraction of gas is 0.001-0.005%.
Deoxidation process is specially to pass through the mixed mixed gas of step S042 by 350 bottom lower head of deoxidation reactor Distribution is described mixed mixed by step S042 to several heat exchanger tubes 353 after the air inlet 357 of 352-2 enters atmolysis cylinder 354 Deoxidation catalyst heat exchange of the coal gas from bottom to top between heat exchanger tube 353 is closed, the process step S042 after heat exchange is mixed mixed It closes coal gas and goes out the deoxidation catalyst progress deoxygenation reaction across heat exchanger tube 353 from top to bottom, deoxygenation reaction after heat exchanger tube 353 Afterwards, gas is discharged by gas outlet 358.Preferably, when the deoxidation reactor 350 exceeds safety value, relief valve 359 is beaten automatically It opens, the gas in deoxidation reactor 350 is discharged by relief valve 359.If the deoxidation reactor is using atmolysis cylinder 354 and uniformly distributed Dry heat exchanger tube guarantees to be evenly distributed by the mixed mixed gas deoxidation of step S042 and deoxidation catalyst, improves deoxygenation Temperature while efficiency in entire deoxidation reactor is uniform, by the way that catalyst self-unloading mouth is arranged, realizes deoxidation catalyst Self-unloading reduces the labor intensity of deoxidation catalyst discharging.
S044), blending and fine de-sulfur: the deoxidation coal gas after step S043 deoxidation is divided into two steps point, a part Deoxidation coal gas after deoxidation carries out after circulating air water cooler 303 cools to 35-45 DEG C by circulating air liquid separation tank 370 Gas-liquid separation, the gas after gas-liquid separation is after converter and/or blast furnace gas recycle compressor are pressurized to 0.93-0.98Mpa As the deoxidation circulating gas in step S042 and converter and/or blast furnace gas blending after step S041 desulfurization, guarantee In mixed mixed gas, the volume fraction of oxygen is not more than 0.7%, the liquids recovery after gas-liquid separation;Another part is de- The deoxidation coal gas that deoxidation coal gas after oxygen is 0.001-0.005% as the volume fraction of the oxygen in step S041 passes through converter Gas change heater 301 and converter and/or blast furnace gas heat exchange are cooling by purified gas water cooler 304 after being cooled to 130-150 DEG C Enter fine de-sulfur tower desulfurization after to 35-45 DEG C, remove mercaptan and dimethyl disulphide remaining in gas, forms purified gas, The total sulfur content of the purified gas is not higher than 0.1mg/Nm3
Preferably, circulating fan, the circulating fan and the converter and/or blast furnace gas recycle compressor are provided with 360 are arranged in parallel, and control in mixed mixed gas, and the volume fraction of oxygen is not more than 0.7%, by the de- of step S043 Deoxidation gas temperature after oxygen is not higher than 160 DEG C.Since coal gas of converter oxygen content is higher, and oxygen content fluctuation is larger, by setting Circulating fan is set, entrance oxygen content is reduced, the deoxidation catalyst realized in deoxidation reactor is long-term at a lower temperature Stable operation.
Preferably, converter and/or blast furnace gas deoxygenation fine de-sulfur go into operation when starting, and before step S041, heating is described to be turned Furnace and/or blast furnace gas are to 55-65 DEG C, to improve the desulfurization effect of converter and/or blast furnace gas;Before step S043, heating Mixed mixed gas is to 55-65 DEG C, to improve deoxidation effect;During normal production, stop heating the converter and/or blast furnace Coal gas and mixed mixed gas.
Preferably, furnace and/or blast furnace gas deoxygenation fine de-sulfur go into operation when starting, control enter step S041 converter and/ Or the mass flow of blast furnace gas is not more than the limiting value that deoxidation reactor is born, here, converter and/or the blast furnace coal of the application The mass flow of gas be 56791-88422kg/h, with guarantee and/or blast furnace gas deoxygenation fine de-sulfur go into operation when starting, control into The mass flow of the converter and/or blast furnace gas that enter step S041 is not more than the limiting value that deoxidation reactor is born.
Before the converter and/or blast furnace gas deoxygenation fine de-sulfur device go into operation, needed before deoxidation catalyst normal use into Row reduction, detailed process is as follows:
A), start converter and/or blast furnace gas recycle compressor 360 and carry out nitrogen circulation, circulation process be converter and/or Blast furnace gas 360 → coal gas of converter of recycle compressor heat exchanger 301 → hydrolysis desulfurization go into operation heater 305 → hydrolysis desulfurizing tower → Go into operation return after heater 302 → deoxidation reactor, 350 → circulating air water cooler 303 → circulating air liquid separation tank 370 converter and/or Blast furnace gas recycle compressor 360.
B), nitrogen is heated to 170-180 DEG C using heater 302 is gone into operation, deoxidation catalyst is finally warming up to 170 DEG C Constant temperature afterwards, then gradually fill into converter and/or blast furnace gas.
Preferably, the heater 305 that needs to go into operation to hydrolysis desulfurization before filling into converter and/or blast furnace gas passes through steam Hydrolysis desulfurizing tower temperature is lifted temperature to 60 DEG C by heating, temperature is then lifted temperature to 180 DEG C, control enters deoxidation reactor 350 CO content, until the volume fraction of CO is to 3-4% and imports and exports CO content and does not change, reduction terminates.
C deoxidation reactor temperature is down to 80 DEG C after) reduction is good, adjusts material gas quantity, starts normal production.
When the converter and/or blast furnace gas deoxygenation fine de-sulfur device are stopped work, gradually reduce and until stop converter and/or Blast furnace gas enters device, starts circulating fan, increases internal circulating load, and deoxidation reactor 350 is changed to circulation process, and circulation process is Converter and/or blast furnace gas 360 → coal gas of converter of recycle compressor heat exchanger 301 → hydrolysis desulfurization go into operation 305 → water of heater It is returned after solution desulfurizing tower → heater 302 → deoxidation reactor, the 350 → circulating air water cooler 303 → circulating air liquid separation tank 370 that goes into operation Rotary furnace and/or blast furnace gas recycle compressor 360 maintain system pressure, are then gradually down to deoxidation catalyst temperature often Temperature stops circulating fan.
After step S0 purification, the flow of coke-stove gas is 78000- for coke-stove gas and converter and/or blast furnace gas 80000Nm3/ h, pressure 3.5-4Mpa, temperature are 38-42 DEG C;In effective component, the volume fraction of methane is 20-25%, hydrogen The volume fraction of gas is 55-60%, and the volume fraction of carbon monoxide is 8-12%, the volume fraction 0.0005-0.0007% of oxygen, The volume fraction of carbon dioxide is 2-4%, and the content of tar and dust is not higher than 0.1mg/Nm3, total sulfur content is not higher than 0.1mg/Nm3;The flow of converter and/or blast furnace gas is 28000-30000Nm3/ h, pressure 0.8-0.85Mpa, temperature are 38-42℃;In effective component, the volume fraction of carbon monoxide is 45-60%, and the volume fraction of carbon dioxide is 20-26%, nitrogen The volume fraction of gas is 20-28%, and the volume fraction of hydrogen is 1-4%, and the volume fraction of oxygen is 0.001-0.005%;Phosphorus The content for changing hydrogen is 100-250mg/kg, and total sulfur content is not higher than 0.1mg/Nm3
S1), converter and/or the thick of blast furnace gas are taken off by the way of pressure-variable adsorption using the thick decarbonization device of pressure-variable adsorption Carbon makes the volume fraction 5.8-6.2% of the carbon dioxide of the converter and/or blast furnace gas by pressure-variable adsorption, hydrogen phosphide Content is 1-5PPM.
The thick decarbonization device of pressure-variable adsorption includes gas-liquid separator 11, and adsorption tower group, purified gas surge tank 13,2 is simultaneously The equalizer tank 14 of connection, water-ring vacuum pump 15, coal gas supply road, vacuumize road, and purified gas buffers road, the road Jun Ya and corresponding Valve group;The adsorption tower group includes 8 adsorption towers 12 in parallel;Coal gas supply road and vacuumize the one end on road with each absorption The bottom of tower 12 is connected to, and the one end on purified gas buffering road and the road Jun Ya is connected to the top of each adsorption tower 12;Gas-liquid separation The gas vent of device 11 is connected to the other end on coal gas supply road, and liquid outlet is connected to liquid withdrawal system;Liquid-ring type vacuum Pump 15 is connected to the other end for vacuumizing road;The entrance of purified gas surge tank 13 is connected to the other end on purified gas buffering road, out Mouth is connected to MDEA solution absorption fine decarbonization device;Each equalizer tank 14 is connected to the other end on the road Jun Ya.Preferably, the suction The multiple-hearth adsorption tower that attached tower 12 is loaded in mixture using common adsorbents and carbon dioxide absorber, in adsorption tower lower part equipped with removing weight Hydro carbons, the proprietary adsorbent of hydrogen phosphide and macromolecular class impurity are equipped with carbon dioxide absorber on adsorption tower top.It is further excellent Choosing, the carbon dioxide absorber is zeolite-type molecular sieves.By the setting of composite bed, it ensure that the two of adsorption tower top Aoxidize the operation steady in a long-term of carbon adsorbent.
The converter and/or the rough decarburization of blast furnace coal and hydrogen phosphide is gone to specifically comprise the following steps:
S11), the liquid warp of the converter and/or blast furnace gas by the completion gas-liquid separation of gas-liquid separator 11, after separation Liquid withdrawal system recycling, converter and/or blast furnace gas after separation enter adsorption tower group.
S12), the adsorption tower group includes 8 adsorption towers in parallel, is adsorbed by the way of the absorption of two towers, when absorption, warp The converter and/or blast furnace gas for crossing step S11 from the entrance of 12 lower part of adsorption tower enter adsorption tower 12, converter and/or blast furnace coal Gas passes through adsorbent bed from bottom to top, and impurity component is adsorbed agent selective absorption, in adsorption cycle, in converter and/or blast furnace gas H2、N2、CO、CH4Equal weakly stables matter component from bottom to top by adsorbent bed, flows out, the purification after decarburization first from adsorption tower top Pneumatic transmission to MDEA solution adsorbs fine decarbonization device, CO in unstripped gas2, hydrogen phosphide and other strong adsorptions are in the impurity component quilt of CO Absorption, as CO in adsorption tower2Concentration reaches predetermined value, when preferably 98%, automatically switches between adsorption tower, the absorption of Previous work Tower decompression enters decompression reproduced state, and the adsorption tower regenerated enters adsorbed state.
The regeneration of the adsorption tower uses five evacuation techniques pressed, and specifically comprises the following steps:
S121), the first stage pressure equilibrium drop (1D, abbreviation one down): after absorption, adsorption tower stops entering converter And/or blast furnace gas, adsorption tower are balanced with the connected progress first time pressure in outlet end with the adsorption tower that two liter steps are completed.
S122), the 2nd stage pressure equilibrium drop (2D, abbreviation two down): after the completion of one down, the outlet end of adsorption tower and Second of the pressure of progress that pressure tank 14 is connected drops.
S123), the equilibrium of 3rd level pressure drop (3D, referred to as three drop): after the completion of two down, adsorption column outlet end with it is complete The progress third time pressure that the input end of the adsorption tower of Cheng Junsheng step is connected drops.
S124), the 4th stage pressure equilibrium drop (4D, referred to as four drop): three drop after the completion of, adsorption column outlet end with it is complete The 4th pressure of progress that the input end of the adsorption tower of Cheng Junsheng step is connected drops.
S125), the 5th stage pressure equilibrium drop (5D, referred to as five drop): four drop after the completion of, adsorption column outlet end with it is complete The 5th pressure of progress that the input end of the adsorbent bed of Cheng Junsheng step is connected drops.
S126), inversely bleed off pressure (D, abbreviation inverse put): after four drop, adsorbent is saturated by impurity in adsorption tower, is led to It crosses reverse depressurization step and residual gas in bed is forward discharged from arrival end, adsorption column pressure drops to close to atmospheric pressure, excellent Choosing, adsorption column pressure drops to 0.02MPa.
S127), evacuate (V): the desorption mode vacuumized using water-ring vacuum pump 15, continue to the bed of adsorption tower into Row decompression, desorbs adsorbent impurity component further, adsorbent achievees the purpose that complete desorption and regeneration.
S128), five~first class pressure equilibrium liter (5~1R, referred to as five~mono- rise): with the adsorption tower that pressurising is completed It is connected with outlet end and carries out the five~pressure equilibrium, while pressurising, bed is extremely empty in the first~five recycling adsorption tower Interior available gas CO component, until pressure balance.
S129), finally boosting (FR, abbreviation final rise): the partial adsorbates of other adsorption tower adsorption step outputs are finally utilized Exhaust gas is by adsorption tower pressurising to working pressure, preferably 0.82MPa.
The 2 towers absorption of 8 adsorption towers in parallel, is pressed for 5 times, and 1 inverse put, 2 times the process vacuumized is as shown in the table:
After thick decarburization, the flow of the converter and/or blast furnace gas is 28000-30000Nm3/ h, pressure 0.75- 0.85Mpa, temperature are 38-42 DEG C;In effective component, the volume fraction of carbon monoxide is 55-65%, the volume point of carbon dioxide Rate is 5.8-6.2%, and the volume fraction of nitrogen is 28-32%, and the volume fraction of hydrogen is 1-4%, and the volume fraction of oxygen is 0.001-0.005%;The content of hydrogen phosphide is 1-5PPM, and total sulfur content is not higher than 0.1mg/Nm3
S2), it is described using the decarbonization device of coke-stove gas and converter and/or blast furnace gas to the coke-stove gas and converter And/or blast furnace gas decarburization, the flow 78000-80000Nm of the coke-stove gas after making decarburization3/ h, pressure 3.5-4Mpa, Temperature is 38-42 DEG C;In effective component, the volume fraction of methane is 20-25%, and the volume fraction of hydrogen is 57-62%, an oxygen The volume fraction for changing carbon is 8-12%, the volume fraction 0.0005-0.0007% of oxygen, and the volume fraction of carbon dioxide is The content of 0.0015-0.0019%, tar and dust is not higher than 0.1mg/Nm3, total sulfur content is not higher than 0.1mg/Nm3;After decarburization Converter and/or blast furnace gas flow be 27000-28500Nm3/ h, pressure 0.7-0.8Mpa, temperature are 38-42 DEG C;Have It imitates in ingredient, the volume fraction of carbon monoxide is 60-70%, and the volume fraction of carbon dioxide is 0.0015-0.0019%, nitrogen Volume fraction be 31-33%, the volume fraction of hydrogen is 1-4%, and the volume fraction of oxygen is 0.001-0.005%;Phosphatization The content of hydrogen is 1-5PPM, and total sulfur content is not higher than 0.1mg/Nm3
The decarbonization device of the coke-stove gas and converter and/or blast furnace gas includes coke oven gas filter 101, coke-oven coal Gas tower top filter 102, rich solution filter 104, coke-stove gas absorption tower 111, regenerator 112, coke-stove gas cooler 121, Poor rich liquid heat exchanger 122, regeneration overhead cooler 123, reboiler 124, lean solution cooler 125, coke-stove gas separator 131, Flash tank 132, lean solution surge tank 133, regeneration overhead gas-liquid separator 134, coke-stove gas lean pump 141, recovery pump 142 turn Furnace and/or blast furnace gas filter 151, converter and/or blast furnace gas tower top filter 152, converter and/or blast furnace gas absorb Tower 161, converter and/or blast furnace gas cooler 171, converter and/or blast furnace gas separator 181 and converter and/or blast furnace coal Gas lean pump 191;The lean solution surge tank 133 is provided with the outlet of the first MDEA lean solution and the outlet of the 2nd MDEA lean solution;Described The outlet of one MDEA lean solution is successively connected to the top entry of coke-stove gas lean pump 141 and coke-stove gas absorption tower 111;The coke The outlet of producer gas filter 101 is connected to the bottom inlet on the coke-stove gas absorption tower 111;The coke-stove gas absorption tower The gas vent at 111 tops is successively connected to the gas access of coke-stove gas cooler 121 and coke-stove gas separator 131, institute The liquid outlet for stating 111 bottom of coke-stove gas absorption tower is connected to 132 entrance of flash tank, the coke-stove gas separator 131 Gas vent is connected to the entrance of the coke-stove gas tower top filter 102, the gas of the coke-stove gas tower top filter 102 Outlet is in communication with the outside, the liquid of coke-stove gas tower top the filter 102 impurity outlet and the coke-stove gas separator 131 The connection of body entrance, the liquid outlet of the coke-stove gas separator 131 are connected to the entrance of flash tank 132;2nd MDEA Top of the lean solution outlet successively with converter and/or blast furnace gas lean pump 191 and converter and/or blast furnace gas absorption tower 161 enters Mouth connection;The outlet of the converter and/or blast furnace gas filter 151 and the converter and/or blast furnace gas absorption tower 161 Bottom inlet connection;The gas vent at the converter and/or the top of blast furnace gas absorption tower 161 successively with converter and/or blast furnace Gas cooler 171 is connected to the gas access of converter and/or blast furnace gas separator 181, the converter and/or blast furnace gas The liquid outlet of 161 bottom of absorption tower is connected to 132 entrance of flash tank, the gas of the converter and/or blast furnace gas separator 181 Body outlet is connected to the entrance of the converter and/or blast furnace gas tower top filter 152, the converter and/or blast furnace gas tower The gas vent of top filter 152 is in communication with the outside, 152 impurity outlet of the converter and/or blast furnace gas tower top filter It is connected to the liquid inlet of the converter and/or blast furnace gas separator 181, the converter and/or blast furnace gas separator 181 Liquid outlet be connected to the entrance of flash tank 132;The top gas outlet of the flash tank 132 is in communication with the outside, the sudden strain of a muscle The liquid outlet of 132 bottom of steaming pot successively with rich solution filter 104, the liquid of poor rich liquid heat exchanger 122 and the top of regenerator 112 Entrance connection;The steam inlet of the reboiler 124 be connected to extraneous steam gas source, the steam (vapor) outlet of the reboiler 124 and The steam inlet of 112 bottom of regenerator is connected to, and the gas vent at 112 top of regenerator is successively cooling with regeneration overhead Device 123 is connected to 134 entrance of regeneration overhead gas-liquid separator, the gas vent of the regeneration overhead gas-liquid separator 134 and outer Boundary's connection, the liquid outlet of the regeneration overhead gas-liquid separator 134 successively connect with the entrance of recovery pump 142 and flash tank 132 It is logical;The liquid outlet of 112 bottom of regenerator is connected to the liquid inlet of the reboiler 124, the reboiler 124 it is molten Successively with poor rich liquid heat exchanger 122, the first MDEA lean solution entrance of lean solution cooler 125 and lean solution surge tank 133 connects for liquid outlet It is logical.
Preferably, the coke-stove gas for being connected to the top entry on coke-stove gas lean pump 141 and coke-stove gas absorption tower 111 is poor Liquid supply road has been arranged in parallel coke-stove gas lean solution filtering supply road, and the coke-stove gas lean solution filtering supply road is provided with Coke-stove gas solution strainer 103.
Preferably, it is connected to the top on converter and/or blast furnace gas lean pump 191 and converter and/or blast furnace gas absorption tower 161 The converter of portion's entrance and/or blast furnace gas lean solution supply road have been arranged in parallel converter and/or the filtering supply of blast furnace gas lean solution Road, the converter and/or blast furnace gas lean solution filtering supply road are provided with converter and/or blast furnace gas solution strainer 153.
Preferably, the coke-stove gas cooler 121, coke-stove gas separator 131 and coke-stove gas tower top filter 102 Setting is at 111 top of coke-stove gas absorption tower;The converter and/or blast furnace gas cooler 171, converter and/or blast furnace Coal gas separator 181 and converter and/or the setting of blast furnace gas tower top filter 152 are absorbed in the converter and/or blast furnace gas 161 top of tower.
Preferably, the regeneration overhead cooler 123 and regeneration overhead gas-liquid separator 134 are arranged in the regenerator 112 tops.
Preferably, the MDEA lean solution for being exported and being gone out by the first MDEA lean solution of lean solution surge tank 133 is poor by coke-stove gas Liquid pump 141 is divided into two-way after boosting, and converges entrance with another way after 103 impurity screening of coke-stove gas solution strainer all the way Coke-stove gas absorption tower 111;By lean solution surge tank 133 the 2nd MDEA lean solution outlet and go out MDEA lean solution by converter and/ Or it is divided into two-way after the boosting of blast furnace gas lean pump 191, it is filtered all the way by converter and/or blast furnace gas solution strainer 153 Converge with another way into converter and/or blast furnace gas absorption tower after impurity.Road is filtered by setting MDEA lean solution, is improved The quality of MDEA lean solution, while online removing MDEA lean solution impurity is realized, improve efficiency.
Preferably, for guarantee system water balance and facilitate preparation, recycling solution, described device be provided with subterranean reservoir and Solution storage trough.Pass through the preparation that the circulation between subterranean reservoir and solution storage trough completes solution at the initial stage of driving, and part is molten Liquid is stored in spare in subterranean reservoir and solution storage trough;Subterranean reservoir recycles draining liquid and passing through for decarbonization system when driving Submerged pump guarantees the water balance of system to system make-up solution.To avoid solution oxide, draws nitrogen and enter subterranean reservoir and molten Liquid storage tank forms nitrogen envelope.It is further preferred that being quickly to defoam after preventing solution foaming and foaming, it is provided with defoaming agent storage tank, The defoaming agent being stored therein in is flow automatically by static pressure difference or can be rapidly entered in lean solution or rich solution by pressure-actuated mode, is driven Dynamic pressure is provided by the nitrogen after depressurizing.It is further preferred that low-pressure steam needed for reboiler is by out-of-bounds providing, from reboiler Steam condensate out returns out-of-bounds after entering low-pressure steam separator.
The decarbonization method of the coke-stove gas and converter and/or blast furnace gas includes the following steps:
Decarbonization method includes the following steps:
S21), coke-stove gas and converter and/or blast furnace gas filtering, removal of impurities, the pressurization of MDEA lean solution
The coke-stove gas just purified and converter and/or blast furnace gas pass through respectively coke oven gas filter 101 and converter and/ Or blast furnace gas filter 151 removes mechanical admixture and free fluid, by lean solution surge tank 133 the outlet of the first MDEA lean solution and 2nd MDEA lean solution exports and MDEA lean solution out passes through coke-stove gas lean pump 141 and converter respectively and/or blast furnace gas is poor Liquid pump 191 boosts to 4-5Mpa, preferably 4.5Mpa, and the temperature of the MDEA lean solution is 50 DEG C.
S22)、CO2Separation
Enter by the coke-stove gas of step S21 from 111 bottom inlet of coke-stove gas absorption tower, the MDEA lean solution after pressurization Entered by the top entry on coke-stove gas absorption tower 111, coke-stove gas pass through from bottom to top coke-stove gas absorption tower 111 with from upper MDEA lean solution after pressurization under and filler surface reverse flow, mass transfer heat exchange, coke-stove gas in coke-stove gas absorption tower 111 In CO2MDEA lean solution after pressurized is absorbed into liquid phase, and unabsorbed component is absorbed with coke-stove gas from coke-stove gas The gas vent outflow at 111 top of tower, absorbs CO2MDEA rich solution by 111 bottom of coke-stove gas absorption tower liquid outlet stream Out.Wherein, CO is not absorbed2Activative MDEA solution become MDEA lean solution, activative MDEA solution absorb sour gas after be known as MDEA rich solution.
By step S21 converter and/or blast furnace gas from converter and/or 161 bottom inlet of blast furnace gas absorption tower into Enter, the MDEA lean solution after pressurization is entered by the top entry on converter and/or blast furnace gas absorption tower 161, converter and/or blast furnace coal Gas pass through from bottom to top the MDEA lean solution after converter and/or blast furnace gas absorption tower 161 and top-down pressurization converter and/ Or filler surface reverse flow, mass transfer exchange heat in blast furnace gas absorption tower 161, the CO in converter and/or blast furnace gas2It is pressurized MDEA lean solution afterwards is absorbed into liquid phase, and unabsorbed component is with converter and/or blast furnace gas from converter and/or blast furnace gas The gas vent outflow at 161 top of absorption tower, absorbs CO2MDEA rich solution by 161 bottom of converter and/or blast furnace gas absorption tower Liquid outlet outflow.
S23), coke-stove gas and converter and/or blast furnace gas purification
S231), by the coal gas of step S22 and converter and/or blast furnace gas pass through respectively coke-stove gas cooler 121 and Converter and/or blast furnace gas cooler 161 cool to 40 DEG C.
S232), pass through coke-stove gas separator respectively by the coke-stove gas of step S231 and converter and/or blast furnace gas 131 and converter and/or blast furnace gas separator 181 complete gas-liquid separation.
S233), by the coke-stove gas of step S232 and converter and/or blast furnace gas respectively by coke-stove gas separator 131 and the gas vent at converter and/or the top of blast furnace gas separator 181 flow out and respectively enter coke-stove gas absorption tower 111 Converter and/or blast furnace gas tower at the top of the coke-stove gas tower top filter 102 at top and converter and/or blast furnace gas absorption tower Top filter 152 separates mechanical admixture and free fluid, completes coke-stove gas and converter and/or the decarburization of blast furnace gas.It is de- The flow of coke-stove gas after carbon is 78000-80000Nm3/ h, pressure 3.5-4Mpa, temperature are 38-42 DEG C;Effective component In, the volume fraction of methane is 20-25%, and the volume fraction of hydrogen is 57-62%, and the volume fraction of carbon monoxide is 8- 12%, the volume fraction 0.0005-0.0007% of oxygen, the volume fraction of carbon dioxide are 0.0015-0.0019%, tar and ash The content of dirt is not higher than 0.1mg/Nm3, total sulfur content is not higher than 0.1mg/Nm3.The stream of converter and/or blast furnace gas after decarburization Amount is 27000-28500Nm3/ h, pressure 0.7-0.8Mpa, temperature are 38-42 DEG C;In effective component, the volume of carbon monoxide Dividing rate is 60-70%, and the volume fraction of carbon dioxide is 0.0015-0.0019%, and the volume fraction of nitrogen is 31-33%, hydrogen The volume fraction of gas is 1-4%, and the volume fraction of oxygen is 0.001-0.005%;The content of hydrogen phosphide is 1-5PPM, and total sulfur contains Amount is not higher than 0.1mg/Nm3
S24), MDEA lean solution circular regeneration
S241), the mechanical admixture isolated in the liquid and step S233 of step S232 separation and free fluid mixing, Meanwhile the MDEA rich solution in step S22 is depressurized to 0.5Mpa by pressure regulator valve.
S242), the MDEA of the liquid mixture and decompression of the liquid in step S241 and mechanical admixture and free fluid Rich solution enters the flash distillation of flash tank 132.
S243), flowed out in flash tank 132 because decompression flashed gas is exported from the top gas of flash tank 132, warp Diffusion system is gone to diffuse after regulating valve control pressure;Preferably, to guarantee that 132 pressure of flash tank is stable and avoids solution oxide, Draw nitrogen and enters flash tank 132 to form nitrogen envelope.It is filtered by the liquid that the liquid outlet of 132 bottom of flash tank flows out by rich solution Formation MDEA rich solution changes by poor rich liquid heat exchanger 122 and MDEA lean solution and is warming up to 98 DEG C after 104 filtering and removing mechanical admixture of device Enter 122 top of regenerator afterwards.
S244), regenerator 122 completes the regeneration to activative MDEA solution by the way of positive pressure air lift, and detailed process is The liquid inlet at MDEA rich solution from 122 top of regenerator enters, and stripping vapor enters from the steam inlet of 122 bottom of regenerator, MDEA rich solution passes through regenerator 112, filler surface and stripping vapor reverse flow from bottom to top in regenerator 112 It moves, carry out sufficient mass-and heat-transfer, the sour gas in MDEA rich solution is largely parsed to gas phase and with stripping vapor from again The gas vent outflow at raw 112 top of tower, the MDEA solution after parsing are flowed out by the liquid outlet of 112 bottom of regenerator, are completed The one parsing of the sour gas of MDEA rich solution.
S245), enter reboiler 124 by reboiler liquid inlet by the MDEA solution of step S244 to heat, then boil Steam in device parses the sour gas in MDEA rich solution, completes the secondary parsing of the sour gas of MDEA rich solution, is formed MDEA lean solution;Steam enters regenerator 112 as stripping vapor from the steam (vapor) outlet at 124 top of reboiler, pushes up from regenerator 112 The gas of the gas vent outflow in portion enters again after the regeneration overhead cooler 123 at 112 top of regenerator is cooled to 40 DEG C The regeneration overhead gas-liquid separator 134 at raw 112 top of tower carries out gas-liquid separation, and isolated gas is by regeneration overhead gas-liquid separator 134 top gas vent outflow is vented on the spot, isolated liquid by 134 bottom of regeneration overhead gas-liquid separator liquid outlet It flows out after recovered pump 142 boosts to 0.55Mpa and enters the flash distillation of flash tank 132.Preferably, steady for guarantee 112 pressure of regenerator Determine and avoid solution oxide, draws nitrogen and enter the formation nitrogen envelope of regeneration overhead gas-liquid separator 134.
S246), the MDEA lean solution that step S245 is formed passes through again after first passing through poor rich liquid heat exchanger 122 and rich solution heat exchange cooling It crosses after lean solution cooler 125 is cooled to room temperature and enters lean solution surge tank 133.
S3), synthesizing glycol coproduction LNG
S31), by the coke-stove gas of step S2 will collect after cryogenic separation goes out LNG, while isolating purity and being 95-97%, pressure are the H of 3.3-3.5MPA2It is 60-70% with the purity isolated, pressure is the rich CO of 0.3-0.4MPa;Institute Stating cold separation technology is the prior art.
S32), the H for isolating step S312Purify out the H that purity is 99%2
S33), will be purified out after the converter of step S2 and/or blast furnace gas are mixed with the rich CO that step S31 is isolated The CO that purity is 98%;Preferably, the rich CO isolated by the converter of step S2 and/or blast furnace gas and step S31 Before mixing, the converter and/or blast furnace gas by step S2 handle except hydrogen phosphide, the converter by step S2 is avoided And/or un-cleared hydrogen phosphide influences the synthetic reaction of ethylene glycol in blast furnace gas, by by step S2 converter and/or Blast furnace gas handle except hydrogen phosphide, makes the content of the intracorporal hydrogen phosphide of gas not higher than 0.1PPM.
S34), extraneous oxygen is introduced and synthesizes DMO with the step S33 CO purified out.
S35), the H for purifying out step S322The DMO synthesizing glycol synthesized with step S34.
Preferably, the content of the CO in step S34 and H in step S352Content ratio be 1:2.
Wherein, synthesis DMO technique can be the prior art, but preferably following techniques:
Dimethyl oxalate (DMO) is by carbon monoxide (CO), methanol (MeOH) and oxygen (O2) synthesis, synthesizing dimethyl oxalate (DMO) reaction equation is as follows:
2CO+1/2O2+2MeOH->DMO+H2O
Pd/Al2O3Make catalyst, reacts synthesis grass with methyl nitrite (MN) catalysis using CO in fixed bed reactors Dimethyl phthalate (DMO), while NO is generated, NO is then converted into MN in MN regenerative response.In DMO synthetic system, fresh CO and warp The circulating air mixing containing MN of compressor pressurization, enters after preheated device preheating equipped with Pd/Al2O3The tubulation of spheric catalyst In formula reactor (DMO reactor).Reaction product is sent into DMO and removes system, to DMO, DMC and other organic matters using methanol into Row is cooling, washs.Thick DMO is sent into DMO distillation system, and circulating air enters MN regenerative system, enters after the pressurization of fraction circulating air Nitrate reductase Tower System.Circulating air and O2Mixing enters from MN regeneration tower bottom, and MeOH enters from the top of regenerator, most of Circulating air enters CO recycle gas compressor and is compressed, and a small amount of gas is sent into exhaust treatment system after recycling MN as periodic off-gases. Regeneration solution of the tower bottom containing nitric acid enters nitrate reductase Tower System.
HNO3It is reacted with NO in circulating air and the MeOH from MN regenerative system and generates MN.
HNO3+2NO+3MeOH→3MN+2H2O
When driving, NO needed for MN regenerative system and nitrate reductase Tower System is generated by sodium nitrite and nitric acid reaction.Nitric acid It restores tower bottoms and enters normal pressure methanol dehydration tower after cooling flash distillation, tower top methanol solution, which is sent to MF knockout tower, further to be separated gently Recycling methanol tank is sent into after component, tower reactor is sent after sodium hydroxide solution neutralizes to high pressure methanol dehydration tower, and high-pressure methanol is de- Water tower tower reactor waste water is sent into waste water treatment system, and tower top methanol and MF knockout tower tower bottoms are sent into recycling methanol tank together.Come Enter DMO distillation system after flashing from the thick DMO (containing methanol, NO and MN etc.) of DMO removing system, flashed vapour is sent at tail gas Reason system recycles MN.Light component in thick DMO separated in lightness-removing column and normal pressure methanol dehydration column overhead methanol solution into Enter MF knockout tower.Tower bottom DMO enters DMC knockout tower, and the thick DMC of tower top is sent to DMC recycle section, and side is adopted DMO and sent to DMO storage tank.
Ethylene glycol synthesis technology can be the prior art, but preferably following techniques:
From H2The fresh hydrogen and H that/CO separator comes2Enter disengaging after the circulating air mixing of recycle gas compressor outlet Pressure saturation in steam heater use is entered after the shell side of material heat exchanger, with the exit gas heat exchange of ethylene glycol synthetic tower out to steam DMO evaporating column lower part is entered after vapour heating.Dimethyl oxalate device come DMO be introduced into DMO surge tank, afterwards by DMO into Enter DMO evaporating column top after material pump pressurization, hydrogen gasifies DMO in DMO evaporating column, and temperature enters after declining 20~35 DEG C Steam heater (I) enters synthetic tower after being heated to 210 DEG C, heater is heated using saturated vapor.All DMO pipelines all use Steam tracing.Ethylene glycol synthetic tower is one " shell-and-tube reactor ", and shell medium is water, and hydrogenation catalyst is in heat exchanger tube. The water being full of in synthetic tower shell side is quickly removed the heat for adding hydrogen to generate.By adjusting water/vapour mixture pressure, control The temperature of hydrogenator shell side, to achieve the purpose that control reaction bed temperature.The high activity copper in ethylene glycol synthetic tower Under the action of series catalysts, Hydrogenation of Dimethyl Oxalate reaction generates ethylene glycol at 210 DEG C.Shell side steam water interface enters drum Afterwards, steam is separated from steam water interface, is sent after pressure stabilizing to steam pipe network.Boiler feedwater is added in drum by pipe network, into And the hydraulic pressure in drum is entered ethylene glycol synthetic tower shell, so that water is completed circulation, so that the heat released in hydrogenation reaction obtains Recycling.Gas after adding hydrogen enters after disengaging material heat exchanger and raw hydrogen heat exchange and carries out gas in high-pressure separator I Liquid separation, gas phase enter synthesis water cooler and are cooled to 40 DEG C, then go through high-pressure separator II and carry out gas-liquid separation again, Most gases enter H2Recycle gas compressor adherence pressure, a small amount of gas are sent to fuel gas pipe network as periodic off-gases.It is high The liquid phase of pressure separator I is entered after pressure reducing valve depressurizes in low-pressure flashing tank I, is then sent to second two by the pressure of itself The methanol distillation column of alcohol rectification section.The liquid phase of high-pressure separator II enters low-pressure flashing tank II after pressure reducing valve depressurizes In, the methanol distillation column of ethylene glycol rectification section is then sent to by the pressure of itself.When crude product needs to be sent in ethylene glycol Between tank field when, the liquid phase of low-pressure flashing tank I first has to be sent in ethylene glycol again after thick ethylene glycol water cooler is cooled to 40 DEG C Between tank field.The flashed vapour of low-pressure flashing tank is sent into fuel gas pipe network or torch.
Wherein, the coke-stove gas decarburization gas vent of decarbonization device successively with CO purifying plant, DMO synthesizer and second The connection of glycol synthesizer, the converter of decarbonization device and/or blast furnace gas decarburization gas vent are connect with cryogenic separation device, deep The coke-stove gas decarburization gas outlet of the CO outlet and decarbonization device of cold separator, the H of cryogenic separation device2Outlet according to Secondary and H2Purifying plant is connected with ethylene glycol synthesizer.
Preferably, the converter of the decarbonization device decarbonization device of the coke-stove gas and converter and/or blast furnace gas and/or height Hydrogen phosphide absorption plant is provided between producer gas decarburization gas vent and CO purifying plant, to the converter Jing Guo step decarburization And/or blast furnace gas handle except hydrogen phosphide, avoids hydrogen phosphide un-cleared in converter and/or the blast furnace gas by decarburization Influence the synthetic reaction of ethylene glycol.
Embodiment 1
A kind of method of coke-stove gas and converter and/or blast furnace gas synthesizing glycol coproduction LNG,
Include the following steps:
S0), coke-stove gas and converter and/or the first purification of blast furnace gas
Just the flow of the coke-stove gas before purification is 83052Nm3/ h, pressure 0.005Mpa, temperature are 20 DEG C;Effectively at In point, the volume fraction of methane is 20.8%, and the volume fraction of hydrogen is 60.31%, and the volume fraction of carbon monoxide is 8.9%, the volume fraction 0.82% of oxygen, the volume fraction of carbon dioxide is 2.58%, and the content of tar and dust is 0.015g/ Nm3, the content of hydrogen sulfide is 50mg/Nm3, the content of other sulfide is 155.2mg/Nm3;The just converter before purification and/or height The flow of producer gas is 29000Nm3/ h, pressure 0.005Mpa, temperature are 20 DEG C;In effective component, the volume of carbon monoxide Dividing rate is 48%, and the volume fraction of carbon dioxide is 24.5%, and the volume fraction of nitrogen is 24.37%, the volume fraction of hydrogen It is 2%, the volume fraction of oxygen is 1%;The content of hydrogen phosphide is 200mg/kg, and the content of tar and dust is 0.015g/ Nm3, the content of sulfide is 17.7mg/Nm3
Coke-stove gas, which goes out to purify, to be included the following steps:
S01), dedusting detar: using electrical tar precipitator to the coke-stove gas dedusting and detar, make the coke-oven coal Dust and tar total amount in gas are not higher than 3mg/Nm3
S02), compress: using helical-lobe compressor compression by the coke-stove gas of step S01 to 0.6Mpa.
S03), thick desulfurization: use rough to the coke-oven coal by step S02 de- by the desulfurizer of desulfurizing agent of iron oxide Sulphur makes the H in coke-stove gas2S content is not higher than 1mg/Nm3
S04), clean: being cleaned, made miscellaneous in coke-stove gas to by the coke-stove gas of step S03 using TSA adsorbent equipment Matter content is not higher than 0.1mg/Nm3;The impurity is arsenic, tar, dust, naphthalene, benzene, one of hydrogen cyanide and ammonia or a variety of groups It closes.
S05), second-compressed: using centrifugal compressor compression by the coke-stove gas of step S04 to 4Mpa.
S06), deoxygenation fine de-sulfur
S061), the coke-stove gas heat exchange of compression heat exchange heating: is warming up to 250 DEG C using First Heat Exchanger 610;
S062), it is anti-that the coke-stove gas after heat exchange heating pre- hydro-conversion and level-one hydro-conversion: is passed sequentially through into pre-add hydrogen Device 100 and level-one hydrogenator 200 is answered to carry out pre- hydro-conversion and level-one hydro-conversion, by the coke-oven coal after heat exchange heating Organic sulfur conversion in gas is hydrogen sulfide, by the oxygen hydrogenation and removing in the coke-stove gas after heat exchange heating, after heat exchange heating Hydrogenation of unsaturated hydrocarbons saturation in coke-stove gas, the impurity in coke-stove gas after removal heat exchange heating;The organic sulfur is COS、CS2、CH3SSCH3, one of methyl mercaptan or multiple combinations;The impurity is arsenic, tar, dust, stupid, naphthalene, ammonia, hydrogen cyanogen One of acid or multiple combinations.
S063), first grade desulfurizing: one will be carried out by first grade desulfurizing reaction unit 300 by the coke-stove gas of step S062 Grade desulfurization, removes inorganic sulfur and hydrogen chloride.Preferably, the first grade desulfurizing reaction unit 300 is moderate temperature desulphurization slot, removes level-one The inorganic sulfur and hydrogen chloride in coke-stove gas after adding hydrogen;The inorganic sulfur is hydrogen sulfide.
S064), secondary heat exchange heats up: will be warming up to 320 by the heat exchange of the second heat exchanger 620 by the coke-stove gas of S063 ℃。
S065), secondary hydrogenation converts: will be carried out by the coke-stove gas of S064 by secondary hydrogenation reactor 400 secondary Hydrogenation reaction will be converted by organic sulfur turn, unsaturated hydrocarbons and oxygen deep hydrogenation remaining in the coke-stove gas of S064, i.e., by two The organic sulfur conversion in coke-stove gas after secondary heat exchange heating is hydrogen sulfide, the oxygen in coke-stove gas after secondary heat exchange is heated up Hydrogenation and removing, the hydrogenation of unsaturated hydrocarbons saturation in the coke-stove gas after secondary heat exchange is heated up.
S066), second level fine de-sulfur: the coke-stove gas after secondary hydrogenation is converted passes through second level fine de-sulfur reaction unit 500 Second level fine de-sulfur is carried out, the total sulfur controlled in gas is removed to not higher than 0.1PPM, and after third heat exchanger 630 is warming up to Continuous process required temperature.
The flow of coke-stove gas after step S066 is 79161Nm3/ h, pressure 3.8Mpa, temperature are 40 DEG C;Have It imitates in ingredient, the volume fraction of methane is 21.31%, and the volume fraction of hydrogen is 58.46%, and the volume fraction of carbon monoxide is 9.12%, the volume fraction 0.0006% of oxygen, the volume fraction of carbon dioxide is 2.64%, and the content of tar and dust is not higher than 0.1mg/Nm3, total sulfur content is not higher than 0.1mg/Nm3
Converter and/or blast furnace gas, which just purify, to be included the following steps:
S01), dedusting detar: using electrical tar precipitator to the converter and/or dedusting of blast furnace gas and detar, make Dust and tar total amount in the converter and/or blast furnace gas are not higher than 3mg/Nm3
S02), compress: compressing the converter for passing through step S01 and/or blast furnace gas using reciprocating compressor to 1Mpa.
S03), clean: using alternating temperature carbon adsorption device, converter and/or blast furnace gas removal of impurities to step S02 make described Impurity content in converter and/or blast furnace gas is not higher than 0.1mg/Nm3
S04), deoxygenation fine de-sulfur: removed using deoxygenation fine de-sulfur device to by the converter and/or blast furnace gas of step S03 Oxygen fine de-sulfur makes the total sulfur content in the coke-stove gas not higher than 0.1mg/Nm3, the volume fraction of oxygen is 0.003%.
The deoxygenation fine de-sulfur includes the following steps:
S041), desulfurization: the body of the converter and/or the blast furnace gas oxygen after coal gas of converter heat exchanger 301 and deoxidation Deoxidation coal gas heat exchange of the integration rate no more than 0.7% enters hydrolysis desulfurizing tower removing organic sulfur and inorganic sulfur after being warming up to 60 DEG C.
S042), mix: the volume fraction by converter and/or blast furnace gas and oxygen after step S041 desulfurization is 0.003% deoxidation circulating gas mixing, controls in mixed mixed gas, and the volume fraction of oxygen is not more than 0.7%.
S043), the mixed mixed gas deoxidation of step S042, the oxygen of the deoxidation coal gas after making deoxidation deoxidation: will be passed through The volume fraction of gas is 0.003%.
S044), blending and fine de-sulfur
Deoxidation coal gas after step S043 deoxidation is divided into two steps point, and the deoxidation coal gas after a part of deoxidation passes through Circulating air water cooler 303 cools to after 40 DEG C and carries out gas-liquid separation by circulating air liquid separation tank 370, the gas after gas-liquid separation Body is after converter and/or blast furnace gas recycle compressor are pressurized to 0.95Mpa as the deoxidation circulating gas in step S042 Converter and/or blast furnace gas blending with after step S041 desulfurization, guarantee in mixed mixed gas, the volume of oxygen Rate is divided to be not more than 0.7%, the liquids recovery after gas-liquid separation;Deoxidation coal gas after another part deoxidation is as in step S041 The deoxidation coal gas that the volume fraction of oxygen is 0.003% is by coal gas of converter heat exchanger 301 and converter and/or blast furnace gas heat exchange Enter fine de-sulfur tower desulfurization after being cooled to 140 DEG C after purified gas water cooler 304 is cooled to 40 DEG C, removes remaining in gas Mercaptan and dimethyl disulphide, form purified gas, and the total sulfur content of the purified gas is not higher than 0.1mg/Nm3
The flow of first purified converter and/or blast furnace gas is 29000Nm3/ h, pressure 0.82Mpa, temperature 40 ℃;In effective component, the volume fraction of carbon monoxide is 48.48%, and the volume fraction of carbon dioxide is 24.75%, nitrogen Volume fraction is 24.62%, and the volume fraction of hydrogen is 2.02%, and the volume fraction of oxygen is 0.003%;The content of hydrogen phosphide For 200mg/kg, total sulfur content is not higher than 0.1mg/Nm3
S1), converter and/or the thick decarburization of blast furnace gas
To the converter and/or the rough decarburization of blast furnace coal and remove hydrogen phosphide using the thick decarbonization device of pressure-variable adsorption, make by The volume fraction of the carbon dioxide of the converter and/or blast furnace gas of pressure-variable adsorption is 6%, and the content of hydrogen phosphide is 3PPM.
The converter and/or the rough decarburization of blast furnace coal specifically comprise the following steps:
S11), the liquid warp of the converter and/or blast furnace gas by the completion gas-liquid separation of gas-liquid separator 11, after separation Liquid withdrawal system recycling, converter and/or blast furnace gas after separation enter adsorption tower group.
S12), the adsorption tower group includes 8 adsorption towers in parallel, is adsorbed by the way of the absorption of two towers, when absorption, warp The converter and/or blast furnace gas for crossing step S11 enter adsorption tower from the entrance of 12 lower part of adsorption tower under the pressure of 0.82Mpa 12, converter and/or blast furnace gas pass through adsorbent bed from bottom to top, and impurity component is adsorbed agent selective absorption, in adsorption cycle, turn H in furnace and/or blast furnace gas2、N2、CO、CH4Equal weakly stables matter component is first from bottom to top by adsorbent bed, from adsorption tower top Outflow, purification pneumatic transmission to the MDEA solution after decarburization adsorb fine decarbonization device, CO in unstripped gas2, hydrogen phosphide and other adsorptivities The impurity component for being better than CO is adsorbed under the pressure of 0.82Mpa, as CO in adsorption tower2When concentration reaches 98%, adsorption tower it Between automatically switch, the decompression of the adsorption tower of Previous work enters decompression reproduced state, and the adsorption tower regenerated enters adsorbed state.
After step S1, the flow of the converter and/or blast furnace gas is 18147Nm3/ h, pressure 0.8Mpa, temperature Degree is 40 DEG C;In effective component, the volume fraction of carbon monoxide is 60.39%, and the volume fraction of carbon dioxide is 6%, nitrogen Volume fraction be 30.97%, the volume fraction of hydrogen is 2.55%, and the volume fraction of oxygen is 0.0038%;Hydrogen phosphide Content is 3PPM, and total sulfur content is not higher than 0.1mg/Nm3
S2), coke-stove gas and converter and/or the decarburization of blast furnace gas
Using MDEA solution absorption decarbonization device to the coke-stove gas decarburization by just purifying, while to by thick decarburization Converter and/or blast furnace gas decarburization make the volume fraction 0.0018% of the carbon dioxide of coke-stove gas, converter and/or blast furnace The volume fraction of the carbon dioxide of coal gas is 0.0017%.
The coke-stove gas and converter and/or the decarburization of blast furnace gas, specifically comprise the following steps:
S21), to converter and/or blast furnace gas filtering, removal of impurities, the pressurization of MDEA lean solution
Coke-stove gas by just purifying and the converter Jing Guo thick decarburization and/or blast furnace gas pass through coke-stove gas respectively Filter 101 and converter and/or blast furnace gas filter 151 remove mechanical admixture and free fluid, by lean solution surge tank 133 The MDEA lean solution that the outlet of first MDEA lean solution and the 2nd MDEA lean solution export and go out is passed through coke-stove gas lean pump 141 respectively and is turned Furnace and/or blast furnace gas lean pump 191 boost to 4.5Mpa, and the temperature of the MDEA lean solution is 50 DEG C.
S22)、CO2Separation
Enter by the coke-stove gas of step S1 from 111 bottom inlet of coke-stove gas absorption tower, the MDEA lean solution after pressurization Entered by the top entry on coke-stove gas absorption tower 111, coke-stove gas pass through from bottom to top coke-stove gas absorption tower 111 with from upper MDEA lean solution after pressurization under and filler surface reverse flow, mass transfer heat exchange, coke-stove gas in coke-stove gas absorption tower 111 In CO2MDEA lean solution after pressurized is absorbed into liquid phase, and unabsorbed component is absorbed with coke-stove gas from coke-stove gas The gas vent outflow at 111 top of tower, absorbs CO2MDEA rich solution by 111 bottom of coke-stove gas absorption tower liquid outlet stream Out.Wherein, CO is not absorbed2Activative MDEA solution become MDEA lean solution, activative MDEA solution absorb sour gas after be known as MDEA rich solution.
By step S1 converter and/or blast furnace gas from converter and/or 161 bottom inlet of blast furnace gas absorption tower into Enter, the MDEA lean solution after pressurization is entered by the top entry on converter and/or blast furnace gas absorption tower 161, converter and/or blast furnace coal Gas pass through from bottom to top the MDEA lean solution after converter and/or blast furnace gas absorption tower 161 and top-down pressurization converter and/ Or filler surface reverse flow, mass transfer exchange heat in blast furnace gas absorption tower 161, the CO in converter and/or blast furnace gas2It is pressurized MDEA lean solution afterwards is absorbed into liquid phase, and unabsorbed component is with converter and/or blast furnace gas from converter and/or blast furnace gas The gas vent outflow at 161 top of absorption tower, absorbs CO2MDEA rich solution by 161 bottom of converter and/or blast furnace gas absorption tower Liquid outlet outflow.
S23), gas purification
S231), by the coal gas of step S22 and converter and/or blast furnace gas pass through respectively coke-stove gas cooler 121 and Converter and/or blast furnace gas cooler 161 cool to 40 DEG C.
S232), pass through coke-stove gas separator respectively by the coke-stove gas of step S231 and converter and/or blast furnace gas 131 and converter and/or blast furnace gas separator 181 complete gas-liquid separation.
S233), by the coke-stove gas of step S232 and converter and/or blast furnace gas respectively by coke-stove gas separator 131 and the gas vent at converter and/or the top of blast furnace gas separator 181 flow out and respectively enter coke-stove gas absorption tower 111 Converter and/or blast furnace gas tower at the top of the coke-stove gas tower top filter 102 at top and converter and/or blast furnace gas absorption tower Top filter 152 separates mechanical admixture and free fluid, completes coke-stove gas and converter and/or the decarburization of blast furnace gas.It is de- The flow of coke-stove gas after carbon is 79113Nm3/ h, pressure 3.75Mpa, temperature are 40 DEG C;In effective component, the body of methane Integration rate is 22.27%, and the volume fraction of hydrogen is 61.1%, and the volume fraction of carbon monoxide is 9.53%, the volume point of oxygen Rate 0.0006%, the volume fraction of carbon dioxide are 0.0018%, and the content of tar and dust is not higher than 0.1mg/Nm3, total sulfur Content is not higher than 0.1mg/Nm3.The flow of converter and/or blast furnace gas after decarburization is 28147Nm3/ h, pressure 0.75Mpa, Temperature is 40 DEG C;In effective component, the volume fraction of carbon monoxide is 64.24%, and the volume fraction of carbon dioxide is 0.0017%, the volume fraction of nitrogen is 32.95%, and the volume fraction of hydrogen is 2.72%, and the volume fraction of oxygen is 0.004%;The content that the content of hydrogen phosphide is no more than hydrogen phosphide is 3PPM, and total sulfur content is not higher than 0.1mg/Nm3
S24), MDEA lean solution circular regeneration
S241), the mechanical admixture isolated in the liquid and step S233 of step S232 separation and free fluid mixing, Meanwhile the MDEA rich solution in step S22 is depressurized to 0.5Mpa by pressure regulator valve.
S242), the MDEA of the liquid mixture and decompression of the liquid in step S241 and mechanical admixture and free fluid Rich solution enters the flash distillation of flash tank 132.
S243), flowed out in flash tank 132 because decompression flashed gas is exported from the top gas of flash tank 132, warp Diffusion system is gone to diffuse after regulating valve control pressure;Preferably, to guarantee that 132 pressure of flash tank is stable and avoids solution oxide, Draw nitrogen and enters flash tank 132 to form nitrogen envelope.It is filtered by the liquid that the liquid outlet of 132 bottom of flash tank flows out by rich solution Formation MDEA rich solution changes by poor rich liquid heat exchanger 122 and MDEA lean solution and is warming up to 98 DEG C after 104 filtering and removing mechanical admixture of device Enter 122 top of regenerator afterwards.
S244), regenerator 122 completes the regeneration to activative MDEA solution by the way of positive pressure air lift, and detailed process is The liquid inlet at MDEA rich solution from 122 top of regenerator enters, and stripping vapor enters from the steam inlet of 122 bottom of regenerator, MDEA rich solution passes through regenerator 112, filler surface and stripping vapor reverse flow from bottom to top in regenerator 112 It moves, carry out sufficient mass-and heat-transfer, the sour gas in MDEA rich solution is largely parsed to gas phase and with stripping vapor from again The gas vent outflow at raw 112 top of tower, the MDEA solution after parsing are flowed out by the liquid outlet of 112 bottom of regenerator, are completed The one parsing of the sour gas of MDEA rich solution.
S245), enter reboiler 124 by reboiler liquid inlet by the MDEA solution of step S244 to heat, then boil Steam in device parses the sour gas in MDEA rich solution, completes the secondary parsing of the sour gas of MDEA rich solution, is formed MDEA lean solution;Steam enters regenerator 112 as stripping vapor from the steam (vapor) outlet at 124 top of reboiler, pushes up from regenerator 112 The gas of the gas vent outflow in portion enters again after the regeneration overhead cooler 123 at 112 top of regenerator is cooled to 40 DEG C The regeneration overhead gas-liquid separator 134 at raw 112 top of tower carries out gas-liquid separation, and isolated gas is by regeneration overhead gas-liquid separator 134 top gas vent outflow is vented on the spot, isolated liquid by 134 bottom of regeneration overhead gas-liquid separator liquid outlet It flows out after recovered pump 142 boosts to 0.55Mpa and enters the flash distillation of flash tank 132.Preferably, steady for guarantee 112 pressure of regenerator Determine and avoid solution oxide, draws nitrogen and enter the formation nitrogen envelope of regeneration overhead gas-liquid separator 134.
S246), the MDEA lean solution that step S245 is formed passes through again after first passing through poor rich liquid heat exchanger 122 and rich solution heat exchange cooling It crosses after lean solution cooler 125 is cooled to room temperature and enters lean solution surge tank 133.
S3), synthesizing glycol coproduction LNG
S31), by the coke-stove gas of step S2 will collect after cryogenic separation goes out LNG, the flow of the LNG is 288Nm3/ h, pressure 0.015Mpa, temperature are -162 DEG C;Isolating purity simultaneously is 97%, and pressure is the H of 3.45MPA2With The purity isolated is 66.06%, and pressure is the rich CO of 0.35MPa;The cold separation technology is the prior art.
S32), the H for isolating step S312Purify out the H that purity is 99%2
S33), will be purified out after the converter of step S2 and/or blast furnace gas are mixed with the rich CO that step S31 is isolated The CO that purity is 98%;Preferably, the rich CO isolated by the converter of step S2 and/or blast furnace gas and step S31 Before mixing, the converter and/or blast furnace gas by step S2 handle except hydrogen phosphide, the converter by step S2 is avoided And/or un-cleared hydrogen phosphide influences the synthetic reaction of ethylene glycol in blast furnace gas, by by step S2 converter and/or Blast furnace gas handle except hydrogen phosphide, makes the content of the intracorporal hydrogen phosphide of gas not higher than 0.1PPM.
S34), extraneous oxygen is introduced and synthesizes DMO with the step S33 CO purified out.
S35), the H for purifying out step S322The DMO synthesizing glycol synthesized with step S34.
In the description of this specification, reference term " one embodiment ", " some embodiments ", " illustrative examples ", The description of " example ", " specific example " or " some examples " etc. means specific features described in conjunction with this embodiment or example, knot Structure, material or feature are contained at least one embodiment or example of the utility model.In the present specification, to above-mentioned art The schematic representation of language may not refer to the same embodiment or example.Moreover, description specific features, structure, material or Person's feature can be combined in any suitable manner in any one or more of the embodiments or examples.
While there has been shown and described that the embodiments of the present invention, it will be understood by those skilled in the art that: These embodiments can be carried out with a variety of variations, modification, replacement in the case where not departing from the principles of the present invention and objective And modification, the scope of the utility model are defined by the claims and their equivalents.

Claims (10)

1. a kind of coke-stove gas and converter and/or blast furnace gas synthesizing glycol coproduction LNG device, it is characterised in that:
Including coke oven gas purifying device, converter and/or blast furnace gas purification plant, the thick decarbonization device of pressure-variable adsorption, coke-oven coal The decarbonization device of gas and converter and/or blast furnace gas, cryogenic separation device, CO purifying plant, H2Purifying plant, DMO synthesis dress It sets and ethylene glycol synthesizer;
Coke oven gas purifying device includes sequentially connected dedusting detar device, compressor, desulfurizer, TSA adsorbent equipment, Compressor and deoxygenation fine de-sulfur device;
Converter and/or blast furnace gas purification plant include sequentially connected dedusting detar device, compressor, TSA adsorbent equipment With deoxygenation fine de-sulfur device;
The outlet of deoxygenation fine de-sulfur device and entering for the thick decarbonization device of pressure-variable adsorption in converter and/or blast furnace gas purification plant Mouth connection;
The outlet of deoxygenation fine de-sulfur device in coke oven gas purifying device and the outlet of the thick decarbonization device of pressure-variable adsorption with Coke-stove gas is connected with the decarbonization device of converter and/or blast furnace gas, and coke-stove gas and converter and/or the decarburization of blast furnace gas fill The coke-stove gas decarburization gas vent set is burnt successively with CO purifying plant, DMO synthesizer and the connection of ethylene glycol synthesizer The converter of the decarbonization device of producer gas and converter and/or blast furnace gas and/or blast furnace gas decarburization gas vent and cryogenic separation Device connection, the coke-stove gas decarburization gas outlet of the CO outlet and decarbonization device of cryogenic separation device, cryogenic separation dress The H set2Outlet successively with H2Purifying plant is connected with ethylene glycol synthesizer.
2. the apparatus according to claim 1, it is characterised in that:
The thick decarbonization device of pressure-variable adsorption includes gas-liquid separator, adsorption tower group, purified gas surge tank, equalizer tank, vacuum pump, coal gas Road is supplied, road is vacuumized, purified gas buffers road, the road Jun Ya;Coal gas supply road and vacuumize the one end on road with adsorption tower group bottom The one end on portion's connection, purified gas buffering road and the road Jun Ya is connected to adsorption tower group top;The gas vent of gas-liquid separator with Coal gas supplies the other end connection on road, and liquid outlet is connected to liquid withdrawal system;Vacuum pump connects with the other end for vacuumizing road It is logical;The entrance of purified gas surge tank is connected to the other end on purified gas buffering road, and fine decarbonization device is adsorbed with MDEA solution in outlet Connection;Equalizer tank is connected to the other end on the road Jun Ya.
3. the apparatus according to claim 1, it is characterised in that:
The decarbonization device of coke-stove gas and converter and/or blast furnace gas includes coke oven gas filter, the filtering of coke-stove gas tower top Device, rich solution filter, coke-stove gas absorption tower, regenerator, coke-stove gas cooler, poor rich liquid heat exchanger, regeneration overhead are cooling Device, reboiler, lean solution cooler, coke-stove gas separator, flash tank, lean solution surge tank, regeneration overhead gas-liquid separator, coke oven Coal gas lean pump, recovery pump, converter and/or blast furnace gas filter, converter and/or blast furnace gas tower top filter, converter and/ Or blast furnace gas absorption tower, converter and/or blast furnace gas cooler, converter and/or blast furnace gas separator and converter and/or height Producer gas lean pump;
Lean solution surge tank is provided with the outlet of the first MDEA lean solution and the outlet of the 2nd MDEA lean solution;
The outlet of first MDEA lean solution is successively connected to the top entry of coke-stove gas lean pump and coke-stove gas absorption tower;Coke-oven coal The outlet of air filter is connected to the bottom inlet on coke-stove gas absorption tower;Gas vent at the top of coke-stove gas absorption tower is successively Be connected to the gas access of coke-stove gas cooler and coke-stove gas separator, the liquid outlet of coke-stove gas absorb the bottom of the tower with The connection of flash tank entrance, the gas vent of coke-stove gas separator are connected to the entrance of coke-stove gas tower top filter, coke-oven coal The gas vent of gas tower top filter is in communication with the outside, coke-stove gas tower top filter impurity outlet and coke-stove gas separator Liquid inlet connection, the liquid outlet of coke-stove gas separator is connected to the entrance of flash tank;
The outlet of 2nd MDEA lean solution successively with converter and/or blast furnace gas lean pump and converter and/or blast furnace gas absorption tower Top entry connection;The bottom inlet of converter and/or the outlet of blast furnace gas filter and converter and/or blast furnace gas absorption tower Connection;Gas vent at the top of converter and/or blast furnace gas absorption tower successively with converter and/or blast furnace gas cooler and converter And/or the gas access connection of blast furnace gas separator, the liquid outlet and flash distillation of converter and/or blast furnace gas absorb the bottom of the tower The connection of tank entrance, the gas vent of converter and/or blast furnace gas separator and converter and/or blast furnace gas tower top filter enter The gas vent of mouth connection, converter and/or blast furnace gas tower top filter is in communication with the outside, converter and/or blast furnace gas tower top Filter impurity outlet is connected to the liquid inlet of converter and/or blast furnace gas separator, converter and/or blast furnace gas separation The liquid outlet of device is connected to the entrance of flash tank;
The top gas outlet of flash tank is in communication with the outside, and the liquid outlet of flash tank bottom is rich or poor successively with rich solution filter Liquid heat exchanger is connected to the liquid inlet at the top of regenerator;The steam inlet of reboiler is connected to extraneous steam gas source, reboiler Steam (vapor) outlet with regeneration tower bottom steam inlet be connected to, the gas vent at the top of regenerator successively with regeneration overhead cooler It is connected to regeneration overhead gas-liquid separator entrance, the gas vent of regeneration overhead gas-liquid separator is in communication with the outside, regeneration overhead The liquid outlet of gas-liquid separator is successively connected to the entrance of recovery pump and flash tank;Regenerate tower bottom liquid outlet with boil again The liquid inlet of device is connected to, the taphole of reboiler successively with poor rich liquid heat exchanger, lean solution cooler and lean solution surge tank The connection of first MDEA lean solution entrance.
4. the apparatus according to claim 1, it is characterised in that: coke-stove gas deoxygenation fine de-sulfur device, including pass sequentially through The First Heat Exchanger of pipeline connection, pre-hydrotreating reaction device, level-one hydrogenator, first grade desulfurizing reaction unit, the second heat exchange Device, secondary hydrogenation reactor, second level fine de-sulfur reaction unit and third heat exchanger;Pre-hydrotreating reaction device includes structure in parallel Identical pre-hydrogenator I and pre-hydrogenator II;First grade desulfurizing reaction unit includes the identical level-one of structure in parallel Desulfurization reactor I, first grade desulfurizing reactor II and first grade desulfurizing reactor III;Second level fine de-sulfur reaction unit includes knot in parallel The identical two-grade desulfurizing reactor I of structure and two-grade desulfurizing reactor II;Pre-hydrogenator I, pre-hydrogenator II, level-one adds Hydrogen reactor is identical with secondary hydrogenation structure of reactor;First grade desulfurizing reactor I, first grade desulfurizing reactor II, first grade desulfurizing is anti- Device III is answered, two-grade desulfurizing reactor I is identical with II structure of two-grade desulfurizing reactor.
5. device according to claim 4, it is characterised in that: coke-stove gas deoxygenation fine de-sulfur device includes bye-pass, branch It is reacted respectively with the pipeline and connection secondary hydrogenation of connection level-one hydrogenator and first grade desulfurizing reaction unit at pipeline both ends The pipeline connection of device and second level fine de-sulfur reaction unit.
6. device according to claim 4, it is characterised in that: pre-hydrogenator I includes hydrogenator shell plus hydrogen Catalyst discharge port under gas reactor entrance, hydrogenator gas vent, hydrogenator, catalyst on hydrogenator Discharge port, under hydrogenator plus hydrogen oxidant layer, on hydrogenator plus hydrogen oxidant layer, the first screen of hydrogenator, hydrogenation reaction The second screen of device, the first silk screen layer of hydrogenator, the second silk screen layer of hydrogenator, hydrogenator third silk screen layer add The 4th silk screen layer of hydrogen reactor, hydrogenator the first porcelain ball transition zone, hydrogenator the second porcelain ball transition zone, hydrogenation reaction Device third porcelain ball transition zone, the 4th porcelain ball transition zone of hydrogenator, the 5th porcelain ball transition zone of hydrogenator, hydrogenator 6th porcelain ball transition zone, the 7th porcelain ball transition zone of hydrogenator, the 8th porcelain ball transition zone of hydrogenator, under hydrogenator Manhole on manhole and hydrogenator, hydrogenator shell include the upper cover being fixedly connected sequentially, and cylinder-shaped body is under End socket;Hydrogenator gas access is arranged in lower head outer surface and is connected to the inner cavity of lower head, hydrogenator gas Outlet is arranged in upper cover outer surface and is connected to the inner cavity of upper cover, from bottom to top, successively fixed to connect in cylinder-shaped body It is connected to the first screen of hydrogenator, the first silk screen layer of hydrogenator, the second silk screen layer of hydrogenator, hydrogenator Two screens, the 4th silk screen layer of hydrogenator third silk screen layer and hydrogenator;Hydrogenator the first porcelain ball transition zone and Hydrogenator the second porcelain ball transition zone is set gradually from bottom to top, and the setting of hydrogenator the first porcelain ball transition zone is adding hydrogen anti- It answers on the first silk screen layer of device, under hydrogenator plus hydrogen oxidant layer is arranged in hydrogenator the second porcelain ball transition zone and hydrogenation reaction Between the second silk screen layer of device;Hydrogenator third porcelain ball transition zone and the 4th porcelain ball transition zone of hydrogenator from bottom to top according to Secondary setting, hydrogenator third porcelain ball transition zone are arranged on the second silk screen layer of hydrogenator;The 5th porcelain of hydrogenator Ball transition zone and the 6th porcelain ball transition zone of hydrogenator are set gradually from bottom to top, and the 5th porcelain ball transition zone of hydrogenator is set It sets on hydrogenator third silk screen layer, on hydrogenator plus hydrogen oxidant layer is arranged in the 6th porcelain ball transition zone of hydrogenator Between the 4th silk screen layer of hydrogenator;The 8th porcelain ball transition zone of the 7th porcelain ball transition zone of hydrogenator and hydrogenator It sets gradually from bottom to top, the 7th porcelain ball transition zone of hydrogenator is arranged on the 4th silk screen layer of hydrogenator;Add hydrogen anti- Catalyst discharge port under device is answered to be fixedly connected with cylinder-shaped body outer surface and add hydrogen oxidant layer to be connected to under hydrogenator;Add hydrogen Catalyst discharge port is fixedly connected with cylinder-shaped body outer surface and adds hydrogen oxidant layer to be connected to on hydrogenator on reactor;Add Hydrogen reactor lower manhole be fixedly connected with cylinder-shaped body outer surface and with the 4th porcelain ball mistake of hydrogenator in cylinder-shaped body Cross the connection of the space between the second screen of layer and hydrogenator;Manhole is fixed with cylinder-shaped body outer surface on hydrogenator It connects and is connected to the space in cylinder-shaped body between the 8th porcelain ball transition zone of hydrogenator and upper cover.
7. device according to claim 4, it is characterised in that: first grade desulfurizing reactor I includes desulfurization reactor shell, takes off Catalyst discharge port under reaction of Salmon-Saxl device gas access, desulfurization reactor gas vent, desulfurization reactor is catalyzed on desulfurization reactor Agent discharge port, under desulfurization reactor plus hydrogen oxidant layer, on desulfurization reactor plus hydrogen oxidant layer, the first screen of desulfurization reactor, desulfurization are anti- Answer the second screen of device, the first silk screen layer of desulfurization reactor, the second silk screen layer of desulfurization reactor, desulfurization reactor third silk screen layer, The 4th silk screen layer of desulfurization reactor, desulfurization reactor the first porcelain ball transition zone, desulfurization reactor the second porcelain ball transition zone, desulfurization are anti- Answer device third porcelain ball transition zone, the 4th porcelain ball transition zone of desulfurization reactor, the 5th porcelain ball transition zone of desulfurization reactor, desulphurization reaction The 6th porcelain ball transition zone of device, the 7th porcelain ball transition zone of desulfurization reactor, the 8th porcelain ball transition zone of desulfurization reactor, desulfurization reactor Manhole in lower manhole and desulfurization reactor, desulfurization reactor shell include the upper cover being fixedly connected sequentially, cylinder-shaped body and Lower head;Desulfurization reactor gas access is arranged in lower head outer surface and is connected to the inner cavity of lower head, desulfurization reactor gas Body outlet is arranged in upper cover outer surface and is connected to the inner cavity of upper cover, in cylinder-shaped body, from bottom to top, successively fixes It is connected with the first screen of desulfurization reactor, the first silk screen layer of desulfurization reactor, the second silk screen layer of desulfurization reactor, desulfurization reactor Second screen, the 4th silk screen layer of desulfurization reactor third silk screen layer and desulfurization reactor;Desulfurization reactor the first porcelain ball transition zone It is set gradually from bottom to top with desulfurization reactor the second porcelain ball transition zone, desulfurization reactor the first porcelain ball transition zone is arranged in desulfurization On the first silk screen layer of reactor, under desulfurization reactor plus the setting of hydrogen oxidant layer is anti-in desulfurization reactor the second porcelain ball transition zone and desulfurization It answers between the second silk screen layer of device;Desulfurization reactor third porcelain ball transition zone and the 4th porcelain ball transition zone of desulfurization reactor are from bottom to top It sets gradually, desulfurization reactor third porcelain ball transition zone is arranged on the second silk screen layer of desulfurization reactor;Desulfurization reactor the 5th Porcelain ball transition zone and the 6th porcelain ball transition zone of desulfurization reactor are set gradually from bottom to top, the 5th porcelain ball transition zone of desulfurization reactor It is arranged on desulfurization reactor third silk screen layer, on desulfurization reactor plus hydrogen oxidant layer is arranged in the 6th porcelain ball transition of desulfurization reactor Between layer and the 4th silk screen layer of desulfurization reactor;The 8th porcelain ball transition of the 7th porcelain ball transition zone of desulfurization reactor and desulfurization reactor Layer is set gradually from bottom to top, and the 7th porcelain ball transition zone of desulfurization reactor is arranged on the 4th silk screen layer of desulfurization reactor;Desulfurization Catalyst discharge port is fixedly connected with cylinder-shaped body outer surface and adds hydrogen oxidant layer to be connected to under desulfurization reactor under reactor;It is de- Catalyst discharge port is fixedly connected with cylinder-shaped body outer surface and adds hydrogen oxidant layer to be connected to on desulfurization reactor on reaction of Salmon-Saxl device; Desulfurization reactor lower manhole be fixedly connected with cylinder-shaped body outer surface and with the 4th porcelain ball of desulfurization reactor in cylinder-shaped body Space connection between the second screen of transition zone and desulfurization reactor;Manhole and cylinder-shaped body outer surface are solid on desulfurization reactor It is fixed to connect and be connected to the space in cylinder-shaped body between the 8th porcelain ball transition zone of desulfurization reactor and upper cover.
8. the apparatus according to claim 1, it is characterised in that: converter and/or blast furnace gas deoxygenation fine de-sulfur device, including Hydrolyze desulfurizing tower, deoxidation reactor and fine de-sulfur tower;The entrance of hydrolysis desulfurizing tower is connected to converter and/or blast furnace gas gas holder, Outlet be connected to the entrance of deoxidation reactor, deoxidation reactor outlet is arranged two branches, a branch be connected to hydrolyze desulfurization The pipeline connection of tower outlet and deoxidation reactor entrance, another branch are connected to the entrance of fine de-sulfur tower.
9. the apparatus according to claim 1, it is characterised in that: converter and/or blast furnace gas deoxygenation fine de-sulfur device include Coal gas of converter heat exchanger, purified gas water cooler, goes into operation heater and hydrolysis desulfurization goes into operation heater;The setting of coal gas of converter heat exchanger Between the entrance and converter and/or blast furnace gas gas holder of hydrolysis desulfurizing tower, while the setting of coal gas of converter heat exchanger is de- in connection The branch road of oxygen reactor outlet and fine de-sulfur tower entrance, purified gas water cooler are arranged in coal gas of converter heat exchanger and fine de-sulfur tower Between branch road;The branch that goes into operation is provided on the pipeline of the entrance of connection hydrolysis desulfurizing tower and converter and/or blast furnace gas gas holder Road, the heater that goes into operation setting are going into operation on branch road, and connection hydrolysis desulfurizing tower exports and is arranged on the pipeline of deoxidation reactor entrance There is hydrolysis desulfurization to go into operation branch, the hydrolysis desulfurization heater setting that goes into operation goes into operation on branch road in hydrolysis desulfurization;It is connected to deoxidation reactor The branch road of outlet and connection hydrolysis desulfurizing tower outlet and deoxidation reactor entrance pipe, is exported to connection water from deoxidation reactor Desulfurizing tower outlet is solved on the pipeline direction of deoxidation reactor entrance, is disposed with circulating air water cooler, circulating air liquid separation tank With converter and/or blast furnace gas recycle compressor.
10. device according to claim 9, it is characterised in that: deoxidation reactor includes shell, upper cover, lower head, if Dry heat exchanger tube, atmolysis cylinder, manhole pipe orifice, catalyst self-unloading mouth, air inlet, gas outlet and relief valve;Shell and upper cover and under End socket connects and composes pressure shell;Several heat exchanger tubes are set in shell and are fixedly connected with atmolysis cylinder, and atmolysis cylinder is fixedly connected In in lower head, air inlet, gas outlet and catalyst self-unloading mouth are respectively fixedly connected in lower head outer surface, air inlet and divide gas Cylinder entrance connection, atmolysis cylinder outlet are connected to several heat exchanger tubes, are connected to inside gas outlet and catalyst self-unloading mouth and lower head, people Hole nozzle and relief valve are fixedly connected with upper cover outer surface respectively and are connected to upper cover inside.
CN201821189001.5U 2018-07-25 2018-07-25 The device of coke-stove gas and converter and/or blast furnace gas synthesizing glycol coproduction LNG Active CN208562273U (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110819393A (en) * 2019-11-26 2020-02-21 中冶南方都市环保工程技术股份有限公司 Method and device for fine desulfurization and purification of blast furnace gas

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110819393A (en) * 2019-11-26 2020-02-21 中冶南方都市环保工程技术股份有限公司 Method and device for fine desulfurization and purification of blast furnace gas

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