CN208586054U - H2The process units of/CO unstripped gas - Google Patents

Abstract

The utility model relates to a kind of H₂The process units of/CO unstripped gas, comprising: shift-converter is obtained for coal gas to be carried out Partial Transformation reaction containing CO, H₂And N₂Reaction gas；First pressure-swing absorption apparatus, is connected to shift-converter, for isolating the CO in obtained reaction gas by the method for pressure-variable adsorption；Second pressure-swing absorption apparatus is connected to the first pressure-swing absorption apparatus, for separating H to except the gaseous mixture after CO carries out pressure-variable adsorption₂And N₂.Thus blast furnace gas can be prepared into the purpose for meeting required ethylene glycol unstripped gas.The utility model has many advantages, such as that energy-saving and emission-reduction, protection environment, process flow is simple, equipment investment is few and added value is high.

Description

H2/The process units of CO unstripped gas

Technical field

The utility model relates to H₂The process units of/CO unstripped gas, more particularly to one kind by blast furnace gas, coal gas of converter Prepare the process unit of the unstripped gas of synthesizing glycol.

Background technique

In recent years, China's industry persistently rapidly develops, and steel coking industry yield increases year by year, according to State Statistics Bureau Statistical result showed in 2014,2013, China's pig iron yield was up to 7.08 hundred million tons, and up to 4.79 hundred million tons, crude steel produces coke output Amount is up to 7.78 hundred million tons.In these industrial processes, a large amount of coke-stove gas (coking), blast furnace gas (refining can be supervened Iron) and coal gas of converter (steel-making), referred to as " three gas ".These by-product gas total amounts every year up to upper tcm, and in by Year increased trend.Meanwhile blast furnace gas, converter coal can be also generated in the smelting process of other ferrous metal and non-ferrous metal Gas and gas component are similar to the tail gas of blast furnace gas, coal gas of converter.In steel mill " three gas ", blast furnace gas although effective gas Body content is minimum, but its discharge amount is maximum.According to statistics, one ton of pig iron by-product, 1700~2000 cubic metres of blast furnace coals are often produced Gas, blast furnace gas accounts for about 64% in " three gas " secondary energy sources total amount, and oven gas accounts for about 29%, and converter gas accounts for about 7%, therefore blast furnace The effective use of coal gas is the energy-saving most important thing of steel mill.

Blast furnace gas main component are as follows: CO, CO₂, N₂, H₂, CH₄Deng wherein CO content accounts for about 25% or so, CO₂And N₂Contain Amount accounts for 15%, 55%, H respectively₂、CH₄Content it is seldom.Blast furnace gas calorific value is low, only 3300~3800kJ/Nm3.Due to blast furnace CO in coal gas₂, N₂Both it is not involved in burning and generates heat, can not be combustion-supporting, it is generated in a large amount of combustion process on the contrary, also absorbing Heat, cause the theoretical temperature combustion of blast furnace gas relatively low, only 1300 DEG C or so.Unstable combustion under blast furnace gas room temperature Fixed, general industry furnace cannot be single using blast furnace gas as fuel, need to mix with high heating value gases ginsengs such as coke-stove gas or coal gas of converter It uses, but blast furnace gas and coke-stove gas or to be used in mixed way hot-restriking die with coal gas of converter big, not only to burner proposition Requirements at the higher level, and also have different degrees of influence to product quality.Since most of enterprise's blast furnace gas is more than needed, high heating value Coal gas is in short supply, therefore the blast furnace gas diffusing phenomenon of various degrees, this not only pollutes environment, but also waste of energy.I State reaches 61,400,000,000 m in blast furnace gas diffusing amount in 2007³, wherein about 16,400,000,000 m containing CO³、CO₂About 8,000,000,000 m³, it is close to convert into standard coal Ten million ton.With the growth of iron and steel output, blast furnace gas diffusing amount is also increasing.How to efficiently use that these calorific values are low, impurity The blast furnace gas that content is high, yield is huge, purification is difficult, environmental pollution is serious is the problem for requiring to solve both at home and abroad.

Utility model content

That the purpose of the utility model is to provide process flows is simple, equipment investment is few and small power consumption by blast furnace gas, turn Producer gas prepares the technique of the unstripped gas of synthesizing glycol, which is not only able to alleviate domestic energy shortage and blast furnace coal blast Take serious status, and the economy and environmental benefit of blast furnace gas can be further increased.

In order to achieve the above object, utility model people is proposed by a large amount of experience in design investigated on the spot with many years A kind of blast furnace gas is through dedusting removal of impurities, desulfurization, Partial Transformation reaction hydrogen manufacturing, carbon dioxide removal, pressure-variable adsorption separation CO, catalysis The integral process of dehydrogenation deoxidation, Pressure Swing Adsorption hydrogen is reacted, the technique is by whole material and energy match, not only Process flow is enormously simplified, and reduces equipment investment and whole energy consumption, further improves blast furnace gas comprehensive utilization Economic benefit.

Technical solution:

H₂The production method of/CO unstripped gas, includes the following steps:

CO is transformed to H by conversion reaction by coal gas by step 1₂, obtain containing CO, H₂And N₂Reaction gas；

Step 2 isolates the CO in reaction gas that step 1 obtains by the method for pressure-variable adsorption；

Got in step 2 is separated H except the gaseous mixture after CO carries out pressure-variable adsorption by step 3₂And N₂；

The H that the CO and step 3 that step 2 obtains are obtained₂As H₂/ CO unstripped gas.

In one embodiment, the H₂/ CO unstripped gas is for producing ethylene glycol.

In one embodiment, the coal gas includes one of coke-stove gas, blast furnace gas or coal gas of converter Or two kinds of mixing.

In one embodiment, the coal gas is also handled by the first removal of impurities before entering step 1.

In one embodiment, first removal of impurities processing includes: dedusting, dephosphorization, arsenic removal, dehydration, deoxidation, takes off Sulphur or remove CH₄In a step or a few steps combination.

In one embodiment, in the step 2, reaction gas is handled by the second removal of impurities.

In one embodiment, the second removal of impurities processing includes removing CO₂The step of.

In one embodiment, in the step 2, the CO isolated is by third exclusion device.

In one embodiment, the third exclusion device includes dehydrogenation deoxygenation.

H₂The process units of/CO unstripped gas, comprising:

Shift-converter is obtained for coal gas to be carried out Partial Transformation reaction containing CO, H₂And N₂Reaction gas；

First pressure-swing absorption apparatus, is connected to shift-converter, for inhaling the CO in obtained reaction gas by transformation Attached method is isolated；

Second pressure-swing absorption apparatus is connected to the first pressure-swing absorption apparatus, for carrying out transformation to except the gaseous mixture after CO Adsorbing separation H₂And N₂。

In one embodiment, further includes: ethylene glycol reactor, be connected to the first pressure-swing absorption apparatus CO outlet and The H of second pressure-swing absorption apparatus₂Outlet, for reacting synthesizing glycol.

In one embodiment, the shift-converter is connected to coke-stove gas, blast furnace gas or coal gas of converter Import.

In one embodiment, the gas inlet of the shift-converter is also connect with the first exclusion device.

In one embodiment, first exclusion device includes dust-extraction unit, dephosphorization apparatus, arsenic removing apparatus, takes off Water installations, device for deoxidizing, desulfurizer or remove CH₄One or several combinations in device.

In one embodiment, the first pressure-swing absorption apparatus is connected to shift-converter by the second exclusion device.

In one embodiment, second exclusion device includes removing CO₂Device.

In one embodiment, described to remove CO₂Device is absorption process except CO₂Device or absorption method remove CO₂Device.

In one embodiment, the outlet CO on the first pressure-swing absorption apparatus is connected to third exclusion device.

In one embodiment, the third exclusion device includes dehydrogenation deaerating plant.

In addition, needing the unit for having used more pressure-variable adsorption to clean to operate in above-mentioned separation process, transformation is inhaled What the energy that energy consumption is high, the operational transformation of buck frequently results in caused by operating pressure is high during attached was difficult to recycle asks Topic.The utility model is normal adsorption separation process and energy recovery process and certain gas or liquid pressing PROCESS COUPLING Together, energy has been recycled, capacity usage ratio is high, and technical process is simple, the operation cost of pressure-variable adsorption is reduced, from cost Angle has expanded the living space of pressure-variable adsorption.Mainly by by expanding machine, motor, compressor or pump group at Driven by Coaxial Energy recycling system carry out energy regenerating operation, which also has compact-sized, overall efficiency is high, whole set equipment expense and Operating cost is all relatively low, has preferable economic benefit.

In above-mentioned pressure-swing absorption process, method as follows can also be used:

A kind of energy reclaiming method with pressure-variable adsorption includes the following steps: the pressure reduction in working pressure-variable adsorption Gas in the process recycles its energy using expanding machine；It is slow by fluid in the gas access of expanding machine and/or gas outlet Flushing device stabilizes the fluctuation of air pressure；Alternatively, inhibiting the fluctuation of its revolving speed by the rotary resistance device in expanding machine shaft.

The fluid cushion device is selected from one of regulating valve or surge tank or several combinations；Described turns Dynamic resistance device refers to flywheel.

The pressure reduction process refer to pressure, pressurising, displacement, it is with pressure rinse, along put or inverse put etc. there are pressure changes The process of change.

In one embodiment, expanding machine drives electrical power generators, and electric energy caused by generator needs electricity for other Electric energy caused by the equipment or generator of power is by compressor to the gas or liquid for needing to boost in pressure-swing absorption process It is compressed.

By controlling the input current for the motor being connected with compressor to supplement the electric energy of its needs；Battery can be passed through Group or capacitance group stabilize the fluctuation of the electric energy for being input to motor.

In one embodiment, electric energy caused by generator is connected to the grid, and the effect of power grid is flat using carrying capacity Press down the fluctuation of electric energy caused by expanding machine；Electric energy obtained in power grid is used for other equipment for needing electric power, or passes through Compressor compresses the gas for needing to boost in pressure-swing absorption process.

In one embodiment, the shaft of expanding machine and the shaft of motor are coaxially connected, by expanding machine and motor It is common to drive compressor operating.

Based on above-mentioned method, following device can also be used:

A kind of pressure-swing absorption apparatus includes:

1), at least one High Pressure Absorption tower；

2), at least one energy recycle device includes expanding machine in the energy recycle device, for recycling high pressure The energy for the high pressure gas being discharged in adsorption tower；

The gas access of expanding machine and/or gas outlet are connected with fluid cushion device；

Alternatively, rotary resistance device is arranged in the shaft of expanding machine.

The fluid cushion device is selected from one of regulating valve or surge tank or several combinations；Described turns Dynamic resistance device refers to flywheel.

In one embodiment, High Pressure Absorption tower between energy recycle device and low pressure adsorbent tower by connecting.

It in one embodiment, further include having generator in pressure-swing absorption apparatus, expanding machine is connect with generator.

Generator with it is other need to connect using the equipment of electric power or generator drive compressor to pressure-swing absorption process It is middle that the gas to boost or liquid is needed to be compressed.

Generator is connect with power grid, and the effect of power grid is the wave that electric energy caused by generator is stabilized using carrying capacity It is dynamic.

It in one embodiment, further include having compressor and motor in pressure-swing absorption apparatus, and the shaft of expanding machine Be with the shaft of motor it is coaxially connected, compressor operating is driven by expanding machine and motor jointly.

Battery pack or capacitance group are also installed on motor.

Surge tank is additionally provided in the gas access of compressor and/or gas vent.

Compared with general pressure swing absorption process, the method and apparatus of the utility model pressure swing absorption process increase The process of energy regenerating, normal adsorption separation process and energy recovery process and certain gas or liquid pressing process coupling It is combined, has recycled energy, improve the capacity usage ratio of system, reduce the operation cost of pressure-variable adsorption, from cost Angle has expanded the living space of pressure-variable adsorption, and technical process is simple, and safety coefficient is high, and unit automation degree is high, operation letter Just, occupation area of equipment is few, ensure that product purity, ensure that the rate of recovery, flexible operation reduce tower quantity and size.

Beneficial effect

The utility model compared with prior art, there are substantive distinguishing features and marked improvement to be: the utility model proposes A kind of blast furnace gas, coal gas of converter prepare the thinking of the unstripped gas of synthesizing glycol through reaction of high order, are not only blast furnace gas Comprehensive utilization provide a technical strategies, and further improve the economic value of blast furnace gas；This is practical new Type is disclosed to prepare H by blast furnace gas, coal gas of converter₂/ CO unstripped gas technique；It is disclosed by the utility model by blast furnace gas, turn Producer gas prepare that the unstripped gas monoblock type technique of synthesizing glycol is calculated by many experiments, simulation, steel mill is investigated on the spot and The experience in design of many years show that material matching and heat utilization consider from whole technique, optimizes process flow.

Detailed description of the invention

Fig. 1 is process method flow chart；

Fig. 2 is the flow chart of embodiment 1；

Fig. 3 is the flow chart of embodiment 2；

Fig. 4 is a kind of structure chart of energy recycle device applied to pressure-swing absorption process；

Fig. 5 is the structure chart that another is applied to the energy recycle device of pressure-swing absorption process；

Fig. 6 is to be integrated with two tower pressure swing adsorption purge H of energy recycle device₂Device；

Fig. 7 is to be integrated with three tower pressure swing adsorption purge H of energy recycle device₂Device；

Wherein 1 is adsorption tower, and 2 be the level-one of turbo-expander, and 3 be compressor, and 4 be motor, and 5 be to take out air cushion Tank, 6 be vacuum pump, and 7 be reverse gas surge tank, and 8 be inverse put air compressor, and 9 be flywheel, and 10 be capacitance group, and 11 be by compressed gas Body import surge tank, 12 be that surge tank is exported by compressed gas, and 13 be turbine import high-pressure buffering pot, and 14 be turbine outlet high pressure Surge tank, 15 be turbine import low pressure buffer tank, and 16 be turbine outlet low pressure buffer tank, and 17 be the second level of turbo-expander, 18 It is supplied materials gas surge tank, 19 be overhead product gas surge tank, and 20 be level-one turbine outlet heat exchanger, and 21 be that the outlet of second level turbine is changed Hot device.

Specific embodiment

The utility model provides a kind of by blast furnace gas, coal gas of converter preparation H₂The method of/CO unstripped gas, this H₂/CO Unstripped gas can be used for preparing ethylene glycol.

Main step is: coal gas is after dedusting, deimpurity process, using the various miscellaneous of dry removal sulphur or sulfur-bearing Matter, then carry out Partial Transformation reaction and prepare hydrogen, gas is mainly organized as hydrogen, CO, CO at this time₂And nitrogen, it is inhaled using transformation Attached partition method removes CO₂, then use pressure swing adsorption method further the mixed gas separation of CO and hydrogen, nitrogen, it is obtained after separation High concentration CO product gas, through catalysis reaction method removing clout in hydrogen and oxygen, obtain higher concentration CO(15% ~ 70%), the unstripped gas as next step process synthesizing glycol；And the nitrogen and hydrogen of remainder are mentioned through pressure-variable adsorption separation Pure hydrogen, to obtain high concentration hydrogen (30% ~ 85%), and the unstripped gas as next step process synthesizing glycol.This is practical In novel, using Partial Transformation reaction is first carried out, the method for re-grading separates gas components is mainly based upon following consideration: One, conversion reaction is stronger exothermic reaction, and general transformation catalyst is non-refractory, and higher temperature can to urge The reactivity of agent reduces, the service life of catalyst shortens, and excessively high reaction temperature can make catalyst failure, excessively high CO's The meeting of changing concentration difference so that reaction calorific value it is excessive so that reaction after temperature rise it is very high, a kind of convenience and lower-cost side Method is multistage Quench method, but the number of segment of Quench increases meeting so that investment cost and operating cost, energy consumption increase.And it uses advanced The method of row Partial Transformation can make the changing concentration difference of CO relatively low, so that the temperature rise after reaction is less high, reduces and become Change the load and severity of reaction.Two, it in order to which high-purity CO can be obtained in the step of pressure swing adsorption method purifies CO, needs mentioning The CO in gaseous mixture before the step of pure CO₂It removes, and since conversion reaction can generate CO₂, and use and first carry out Partial Transformation Method, can make later a step once take off to obtain whole CO₂, thus under conditions of guaranteeing to obtain high-purity CO, The maintenance expense that occupied area can be reduced, investment cost is reduced, reduce equipment.

H provided by the utility model₂Blast furnace gas, converter coal is mainly utilized in the production method of/CO unstripped gas Gas, coke-stove gas etc. are used as raw material.Oven gas mainly contains methane and hydrogen, can be same as part material with purifying hydrogen of hydrogen Hydrogen blending obtained is converted to use.

Mainly include in the gas composition of above-mentioned coal gas: N₂、H₂、CO、CO₂、O₂、CH₄、H₂S, COS etc., in some allusion quotations In the blast furnace gas of type, composition includes by volume percentage: N₂40~65%, H₂0.5~5%, O₂0.2~5%, CO₂ 10~30%, CO 10~30%, CH₄0.1~2.0%, H₂5~400ppm of S, 0.1~100ppm of COS.Institute in the utility model " the H stated₂/ CO unstripped gas " is primarily referred to as CO and H₂, they are individualisms.H₂The purposes of/CO unstripped gas can be used in difference Catalyst on synthesize different industrial chemicals, this method has obtained pure CO and H₂, can be also used for ethyl alcohol processed, second two processed Alcohol etc. is reacted by chain and CO is added, so that a carbon atom or multiple carbon atoms (carbonylation), need to adjust later Species can carry out adding hydrogen H again when needed₂。H₂/ CO unstripped gas can also be used to produce ethyl alcohol and other pass through addition CO Realize that chain reaction, can when needing to adjust product type later to realize increase one or more carbon atoms (carbonylation) To carry out adding hydrogen H when needed again₂Obtained from product.

The basic principle of CO transformation is:

；

This is the isometric chemical reaction of a reversible heat release, chemically for reaction balance angle, improves pressure to change Learning to balance does not influence, but reduces reaction temperature and increase steam vapour amount in reactant and be conducive to reaction to generation CO₂And H₂'s Direction carries out.0.5~20MPa of its reaction pressure, 160~500 DEG C of reaction temperature.Gas after Partial Transformation reacts mainly contains Hydrogen, nitrogen, carbon monoxide and carbon dioxide and some other trace impurities.Conversion reaction is using copper-based and/or iron-based And/or cobalt-molybdenum series catalyst, catalyst include copper and/or iron and/or zinc and/or aluminium and/or manganese and/or cobalt and/or molybdenum and/or Cerium and/or magnesium and/or chromium and/or potassium and/or vanadium and/or nickel and/or titanium and/or palladium and/or platinum and/or ruthenium and/or rhodium and/or The oxide and/or their vulcanization of sodium and/or rubidium and/or caesium and/or niobium and/or zirconium and/or rare earth element and/or alkali metal Object and/or their soluble-salt and/or the metal composite oxide formed between them.Carrier is active carbon, aluminium oxide, oxygen SiClx, magnesia, titanium oxide, silica gel, molecular sieve, hydrotalcite, spinelle, ceramic honey comb, monazite, honeycomb, metal plate, Ripple packing, corrugated plating, fiber (cloth) material and structure, braided fabric, metal foam, ceramic foam, graphite-based foaming body, Copper and/or iron and/or zinc and/or aluminium and/or manganese and/or cobalt and/or molybdenum and/or cerium and/or magnesium and/or chromium and/or potassium and/or Vanadium and/or nickel and/or titanium and/or palladium and/or platinum and/or ruthenium and/or rhodium and/or sodium and/or rubidium and/or caesium and/or niobium and/or The oxide and/or their sulfide and/or their soluble-salt of zirconium and/or rare earth element and/or alkali metal and/or it Between the metal composite oxide etc. that is formed.The CO of high concentration carries out Partial Transformation reaction and prepares hydrogen reactor using multistage It is insulated shift-converter or intends quasi- isothermal shift-converter, 0.2~20Mpa of reaction pressure, 160~500 DEG C of reaction temperature.By CO Partial Transformation reaction prepares the transformed depth of hydrogen, the supplied materials gas of the external gas source by subsequent process requirements and as supplement CO and/or H₂Quantity and ratio determine.Thus CO and H is adjusted₂Ratio reach the requirement of subsequent technique.

As high concentration H required in the unstripped gas of required synthesizing glycol₂When pressure in gas is higher, for conversion reaction For excessively high pressure may needs higher temperature when not occurring liquid in gas and have certain surplus, it is excessively high Reaction temperature when can be adversely affected to catalyst for water-gas shift reaction, can be converted using suitable pressure and temperature Reaction, and be further pressurized after subsequent decarburization proposes hydrogen process to reach the unstripped gas of required synthesizing glycol and want The pressure asked.

Before carrying out Partial Transformation reaction, removal of impurities processing can be carried out to coal gas, it includes: to remove that removal of impurities here, which can be, Dirt, dephosphorization, arsenic removal, dehydration, deoxidation, desulfurization or remove CH₄In a step or a few steps combination, it is harmful miscellaneous in gas after purification Matter content is controlled in sulfide≤1.15ppm, NH₃≤ 200ppm, H₂≤ 1000ppm, O₂≤ 1000ppm, H₂O≤100ppm。

When in pressure-variable adsorption partition method separation of nitrogen, hydrogen and CO step if the too high levels (such as >=0.5% of oxygen When), in order to protect the adsorbent of CO and nitrogen, hydrogen step, or meet standard (GB3864-2008 and its more if necessary New version) industrial nitrogen when.The content for needing to reduce the oxygen in gas is needed in pressure-variable adsorption partition method separating nitrogen The step of removing the micro amount of oxygen in gas using deoxidier is added in a step or a few steps before gas, hydrogen and CO step.It is described to urge Changing deoxidation step is under the conditions of 0.1~2MPa pressure and 4~1000 DEG C of temperature using in selective deoxidier removing gas O₂.The purity for mentioning the CO for the high concentration that purification CO step obtains is also helped simultaneously.Remove the deoxidation of the micro amount of oxygen in gas Agent can be the catalyzing deoxidation agent reacted with CO, be also possible to chemical absorbing deoxidier.Deoxidier with containing calcium, lead, Sodium, aluminium, potassium, magnesium, titanium, zirconium, vanadium, manganese, iron, nickel, cobalt, copper, molybdenum, tungsten, lanthanum, zinc, silver, palladium, cobalt, rhodium, platinum or cerium metal and/or Their oxide and/or sulfide and/or one or more of the complex compound that they are formed.Carrier is active carbon, oxidation Aluminium, silica, magnesia, titanium oxide, silica gel, molecular sieve, ceramic honey comb, monazite, honeycomb, metal plate, ripple packing, Corrugated plating, fiber (cloth) material and structure, braided fabric, metal foam, ceramic foam, graphite-based foaming body etc..It can be with It is that can also be sulphite using active carbon, aluminium oxide, silica gel, molecular sieve, carbon molecular sieve as the absorption method deoxidier of adsorbent Deoxidier.

Remove sulphur removal or the sulphur contained various impurity can using absorption method, membrane separating method, containing iron or manganese or zinc or It is the solid desulfurating agent of the oxide or hydroxide or the metal composite oxide formed between them of copper or nickel or calcium or tin, low Warm methanol wash method, propylene carbonate ester process, N methylpyrrolidone process, polyglycol dimethyl ether process, polyethylene glycol methyl propyl ether method, Tributyl phosphate method, hot potash method, activation hot potash method, MEA process, DEA process, MDEA method, DIPA method, propylene carbonate ester process+ DIPA, propylene carbonate ester process+glycol amine, sulfolane process, sulfolane+DIPA method, sulfolane+MDEA method, methanol+secondary amine method, alkane Base alkanolamine solution method and MEA process, the DEA process, MDEA method, ammonia scrubbing method, soda processes, ADA method that activating agent is added (stretford method), tannin process, LO-CAT method, Sulferox method, Sulfint method, Konox method, Bio-SR method, naphthoquinones method (Takahax method), metal phthalocyanine method (PDS method), G-V(Giammarco-Vetrocoke process), arsenic alkaline process, MSQ method, Sulfolin method, EDTA method, Wet oxidation process, alkali absorption method, limestone-gypsum method, ammonia process, magnesium processes, phospho-ammonium fertilizer method, organic acid sodium-gypsum, lime- Magnesium processes, calcium method, dry-type circulating fluidized bed method, zinc oxide method, urea method, Absorption via Chemical Complexation, charged dry sorbent injection method, etc. Processes, electronic beam method, Dual alkali, vulcanization alkaline process and their combination.When supplied materials gas contains the content of organic sulfur in sulphur It is excessively high, organic sulfur conversion H2S can be made, then carry out desulfurization by catalytic hydrogenation reaction or catalytic hydrolysis reaction, so that by The sulfur content of treated gas can satisfy requirement.It is mainly SO2 and too high levels when supplied materials gas contains in sulphur, can passes through Catalytic hydrogenation reaction makes SO₂It is converted into H₂S, then desulfurization is carried out, so that the sulfur content of gas after treatment can satisfy and want It asks.Iron and/or copper and/or cobalt and/or manganese and/or molybdenum and/or zinc and/or aluminium of the catalyst of catalytic hydrogenation reaction to contain And/or the metal and/or their oxide and/or their sulfide of nickel and/or titanium and/or zirconium and/or tungsten and/or cerium And/or they soluble-salt and/or the metal composite oxide that is formed between them be active component, with titanium, zirconium, manganese, iron, Nickel, cobalt, copper, molybdenum, tungsten, zinc, cobalt, the metal of cerium and/or their oxide and silicon, rare earth, alkali metal, alkaline-earth metal, mistake Crossing one or more of oxide and/or their sulfide of metal is auxiliary agent.Carrier is active carbon, aluminium oxide, oxidation Silicon, magnesia, titanium oxide, silica gel, molecular sieve, ceramic honey comb, monazite, honeycomb, metal plate, ripple packing, corrugated plating, Fiber (cloth) material and structure, braided fabric, metal foam, ceramic foam, graphite-based foaming body etc..Catalytic hydrolysis reaction Catalyst with the magnesium and/or lanthanum and/or barium and/or aluminium and/or titanium and/or zirconium and/or cerium and/or potassium and/or calcium that contain and/or The metal and/or their oxide of cobalt and/or molybdenum and/or iron and/or copper and/or manganese and/or zinc and/or nickel and/or tungsten and/ Or they sulfide and/or the metal composite oxide that is formed between them be active component, with titanium, zirconium, nickel, cobalt, molybdenum, Cobalt, the metal of cerium and/or their oxide and silicon, rare earth, alkali metal, alkaline-earth metal, transition metal oxide and/or One or more of their sulfide is auxiliary agent.Carrier is active carbon, aluminium oxide, silica, magnesia, titanium oxide, silicon Glue, molecular sieve, ceramic honey comb, monazite, honeycomb, metal plate, ripple packing, corrugated plating, fiber (cloth) material and structure, Braided fabric, metal foam, ceramic foam, graphite-based foaming body etc..Sulphur after desulfurization in gas is removed to 0.01~ 0.1ppm。

After Partial Transformation reaction prepares hydrogen, gas is mainly organized as hydrogen, CO, CO at this time₂And nitrogen.

After carrying out Partial Transformation reaction, it is also desirable to carry out removal of impurities processing, removal of impurities here can be including except CO₂, The method of carbon dioxide removal can use pressure swing adsorption method, absorption process and their combination.Wherein absorption process includes: washing Method, low-temp methanol wash method, propylene carbonate ester process, N methylpyrrolidone process, polyglycol dimethyl ether process, polyethylene glycol methyl-prop Ether method, Catacarb method (catalytic thermal alkaline process), hot potash method, activation hot potash method, improvement thermokalite method, hot carbonate method, amino Hydrochlorate method, ammonia scrubbing method, connection urine (alkali) method, G-V(Giammarco-Vetrocoke process), MEA process, DEA process, MDEA method, DIPA method, TEA method, Sulfolane process, sulfolane+DIPA method, sulfolane+MDEA method, methanol+secondary amine method, alkyl alcoholamine solwution method and addition activating agent MEA process, DEA process, MDEA method, TEA method etc..If separated using Processes of Removing Carbon Dioxide from Mixture Gases by Pressure Swing Adsorption or using pressure-variable adsorption When method separates CO and nitrogen, hydrogen, need that temp.-changing adsorption method, separation removal water are added before the unit of transformation pressure-variable adsorption With the ingredients such as the heavy constituent that contains in some gases.When using the series connection of a set of pressure-swing absorption apparatus is greater than, temp.-changing adsorption separation Unit is added in front of the separative unit of first set pressure swing adsorption method.When using pressure swing adsorption method, it can be filled in pressure-variable adsorption Interior addition energy recycling system is set, recycles the pressure energy wasted in pressure-swing absorption process simultaneously completing pressure-variable adsorption separation process. When using absorption process, absorbent has absorbability to sulphur and carbon dioxide simultaneously, then can remove sulphur and dioxy at the same time Change carbon, when the isolated unit using absorption process as decarburization, it will usually take micro absorbing liquid out of in gas, need Temp.-changing adsorption separative unit is added behind its unit to remove the ingredients such as the heavy constituent contained in water and some gases, removes out The high concentration carbon dioxide come can be directly for sale if the purity requirement needed for meeting or be used for other devices, such as Fruit do not reach requirement can continue purification with reach require, then it is for sale or for other devices use.It is separated through pressure-variable adsorption After method decarburization, CO₂It is removed to 0.01~0.8Vol%.

When use pressure swing adsorption method is from containing CO, H₂、N₂Gas in when isolating CO, using copper-loaded base or carry the suction of silver-based Attached dose or metal organic framework type adsorbent (MOFs, ZIFs), metal-organic polyhedra (MOPs).Carrier can be active carbon, Aluminium oxide, silica gel, molecular sieve, ceramic honey comb, monazite, honeycomb, metal plate, ripple packing, corrugated plating, fiber (cloth) material Material and structure, braided fabric, metal foam, ceramic foam, graphite-based foaming body etc..The adsorptive pressure of pressure-variable adsorption is 0.02 ~2MPa or so, 0~100 DEG C of operation temperature.The mixing of the CO product gas and nitrogen, hydrogen of high concentration obtained after separation Gas.

It needs to meet H in required high concentration CO gas in the unstripped gas of synthesizing glycol₂And O₂Concentration necessary (H₂≤ 1000ppm, O₂≤ 1000ppm), when the high concentration obtained after pressure-variable adsorption partition method separates CO and nitrogen, hydrogen step CO when not reaching requirement, the method for taking catalyzed selective oxydehydrogenation can be added and take off H₂With de- O₂, so that H₂And O₂It is dense Spend meet demand.The method for taking catalysis oxidation takes off H₂With de- O₂Temperature be >=100 DEG C.Palladium and/or platinum of the catalyst to contain And/or the metal and/or their oxide and/or sulfide of cobalt and/or manganese and/or copper be active component, with sodium, potassium, magnesium, Titanium, zirconium, vanadium, manganese, iron, nickel, cobalt, copper, molybdenum, tungsten, lanthanum, zinc, silver, palladium, the metal of cobalt or cerium and/or their oxide and/or One or more of sulfide and/or the complex compound that they are formed are auxiliary agent.Carrier is active carbon, aluminium oxide, silica, oxygen Change magnesium, titanium oxide, silica gel, molecular sieve, ceramic honey comb, monazite, honeycomb, metal plate, ripple packing, corrugated plating, fiber (cloth) material and structure, braided fabric, metal foam, ceramic foam, graphite-based foaming body etc..Catalytic dehydrogenation process be Using the H in selective dehydrogenation catalyst removal blast furnace gas under the conditions of 0.1~10MPa pressure and 50~500 DEG C of temperature₂And O₂。 After pure CO after dehydrogenation deoxidation feeds intermediate air accumulator, the unstripped gas as synthesizing glycol is for next step synthesizing glycol Device uses.Objectionable impurities content is controlled in sulfide≤1.15ppm, NH in pure CO gas after purification₃≤ 200ppm, H₂≤ 1000ppm, O₂≤ 1000ppm, H₂O≤100ppm。

The mixed gas of pressure-variable adsorption nitrogen obtained after separation, hydrogen, then height is obtained through pressure swing adsorption method removing nitrogen Pure H₂.By H after purification₂After being sent into intermediate air accumulator, the unstripped gas as synthesizing glycol is for next step synthesizing glycol Device uses.It is pressure is 1.5~20MPag that it, which adjusts its pressure, and reaction temperature is 180~250 DEG C.By CO from H₂、N₂'s After isolating in gas, through pressure-variable adsorption separating-purifying hydrogen step, the nitrogen and other micro gas components come is removed Gas, can directly for sale or confession if when meeting the industrial nitrogen of standard (GB3864-2008 and its more new version) Other devices use, if do not reach requirement can continue purification with reach require, then it is for sale or for other devices use.

When meeting the industrial nitrogen of standard (GB3864-2008 and its more new version) if necessary, if the blast furnace Coal gas, coal gas of converter and its contain CH with the gaseous mixture of the gas in other sources containing blast furnace gas or coal gas of converter₄, Ke Yijia Enter to take the method for catalysis oxidation to take off CH₄.So that the purity of obtained nitrogen meets industrial nitrogen standard (GB3864-2008 And its more new version).The method for taking catalysis oxidation takes off CH₄Temperature be >=100 DEG C.Used catalyst be containing iron and/or Copper and/or cobalt and/or manganese and/or molybdenum and/or zinc and/or aluminium and/or nickel and/or chromium and/or bismuth and/or magnesium and/or titanium and/or The metal of barium and/or ruthenium and/or zirconium and/or cerium and/or group of the lanthanides and/or platinum and/or palladium and/or gold and/or rhodium and/or calcium and/ Or their oxide and/or their soluble-salt and/or the metal composite oxide formed between them is active component. With titanium, zirconium, manganese, iron, nickel, cobalt, copper, molybdenum, tungsten, zinc, cobalt, cerium, aluminium, chromium, bismuth, magnesium, titanium, barium, ruthenium, zirconium, cerium, lanthanum, platinum, palladium, gold, Rhodium, the metal of calcium and/or their oxide and/or their soluble-salt and/or the composition metal oxygen formed between them One or more of compound and silicon, rare earth, alkali metal, alkaline-earth metal, the oxide of transition metal are auxiliary agent.Carrier is to live Property charcoal, aluminium oxide, silica, magnesia, titanium oxide, silica gel, molecular sieve, ceramic honey comb, monazite, honeycomb, metal plate, Ripple packing, corrugated plating, fiber (cloth) material and structure, braided fabric, metal foam, ceramic foam, graphite-based foaming body Deng.If the H contained in supplied materials gas₂And O₂Or CH₄Content it is sufficiently low when can cancel accordingly catalyst combustion reaction removing methane The step of or catalytic dehydrogenation step.

In above process, such as pressure swing adsorption method separation CO, separation H₂/N₂Deng can be before the unit of pressure-variable adsorption Temp.-changing adsorption separative unit, the ingredients such as heavy constituent contained in separation removal water and some gases are added.When a set of using being greater than When pressure-swing absorption apparatus is connected, temp.-changing adsorption separative unit is added in front of the separative unit of first set pressure swing adsorption method.

Based on above method, the utility model additionally provides H₂The process units of/CO unstripped gas, comprising:

Shift-converter is obtained for coal gas to be carried out Partial Transformation reaction containing CO, H₂And N₂Reaction gas；

First pressure-swing absorption apparatus, is connected to shift-converter, for inhaling the CO in obtained reaction gas by transformation Attached method is isolated；

Second pressure-swing absorption apparatus is connected to the first pressure-swing absorption apparatus, for carrying out transformation to except the gaseous mixture after CO Adsorbing separation H₂And N₂。

In one embodiment, further includes: ethylene glycol reactor, be connected to the first pressure-swing absorption apparatus CO outlet and The H of second pressure-swing absorption apparatus₂Outlet, for reacting synthesizing glycol.

In one embodiment, the shift-converter is connected to coke-stove gas, blast furnace gas or coal gas of converter Import.

In one embodiment, the gas inlet of the shift-converter is also connect with the first exclusion device.

In one embodiment, first exclusion device includes dust-extraction unit, dephosphorization apparatus, arsenic removing apparatus, takes off Water installations, device for deoxidizing, desulfurizer or remove CH₄One or several combinations in device.

In one embodiment, the first pressure-swing absorption apparatus is connected to shift-converter by the second exclusion device.

In one embodiment, second exclusion device includes removing CO₂Device.

In one embodiment, described to remove CO₂Device is absorption process except CO₂Device or absorption method remove CO₂Device.

In one embodiment, the outlet CO on the first pressure-swing absorption apparatus is connected to third exclusion device.

In one embodiment, the third exclusion device includes dehydrogenation deaerating plant.

In the methods described above, it is needed in some separating steps using to pressure-variable adsorption lock out operation；The utility model Purpose is relatively high for supplied materials gas pressure or needs to be pressurized to relatively high situation and be just able to achieve the separation for meeting demand Bigger pressure change process, is frequently going up and down present in the room temperature pressure-variable adsorption of effect and non-room temperature pressure-variable adsorption field During press operation, by had higher pressure energy in the high pressure gas of equipment discharge, there are a large amount of energy loss, institutes for this process It energy recycle device is added during these pressure changes are bigger, recovers energy, the energy of recycling for providing Mechanical energy, for providing pressure to gas or liquid.

The equipment of discharge high pressure gas referred herein in industrialized variable-pressure adsorption equipment there are many, it is most commonly seen Be adsorption tower, be also possible to other vacuum tanks, surge tank, in these equipment have high pressure gas, pressure reduction may be and Another adsorption tower or vacuum tank, surge tank in low-pressure state pressed, pressurising, it is suitable put or the processes such as inverse put, at this During a little, the gas energy that the high pressure gas in adsorption saturation adsorption tower can be recycled through energy recycle device recycling is again Flow to adsorption tower or vacuum tank, surge tank in low-pressure state, be completed at the same time energy recycling and normal pressure-variable adsorption Pressure reduction, energy recycle device here can be converted pressure energy possessed by high pressure gas to when using expanding machine Mechanical energy, these mechanical energy can be applied to drive compressor rotation, engine power generation, supplement motor rotation power output etc. a variety of Purposes.It is all unstable for the decompression gas flow, pressure and the pressure drop that access energy recycle device in pressure-variable adsorption process, With periodical and bigger fluctuation, it will usually cause energy recycle device almost can not normal table work, therefore need Energy recycle device is correspondingly improved.

The major design design of the utility model is: by stabilizing by the periodic quick of the gas of high-pressure installation discharge Fluctuation is can work normally expanding machine, mainly by passing through stream in the gas access of expanding machine and/or gas outlet Body buffer unit stabilizes the fluctuation of air pressure；Another resolving ideas is: by inhibiting wave of the shaft of expanding machine on revolving speed It is dynamic, it also may be implemented to make its even running, can be realized by installing rotary resistance device in its shaft.

Based on above-mentioned design, there are several embodiments below:

The gas for needing energy regenerating enter energy recycle device in turbo-expander before or leave energy return The surge tank of a constant volume is added after receiving apparatus, surge tank can be used to stabilize the pressure of pressurized gas and the wave of flow It is dynamic, keep its basicly stable, the energy for first recycling the middle gas of pressure-variable adsorption by expanding machine may be implemented, be converted into the machinery of axis Energy.

In another embodiment, regulating valve is installed on the gas piping in energy recycle device, by pressing During power changes, according to Pressure change frequencies and size, correspondingly the aperture of regulating valve is adjusted, is expanded to entering The pressure of the high pressure gas of machine and flowed fluctuation are inhibited.

For needing to increase the design of the shaft rotary resistance of expanding machine, in another embodiment, in expanding machine The flywheel of certain size and certain mass distribution is installed to increase the rotary inertia of axis in shaft, the installation site of flywheel can be On the upstream side of expanding machine or the shaft in downstream side.

Above as can be seen that after having used buffer unit or resistance device, when expanding machine switchs to gas pressure energy During mechanical energy, the variation fluctuation of pressure energy can be preferably stabilized, allows the normal smooth working of expanding machine, is also suitable for In mechanical energy is applied to it is other it is each require the expenditure of energy during.

In order to preferably utilize mechanical energy caused by expanding machine, mechanical energy can be driven to other equipment rotation works Make, is recycled after mechanical energy can also being converted to electric energy.

In one embodiment, motor is driven to generate electricity in expanding machine, since the rotation of expanding machine has centainly Cyclic fluctuation variation, therefore the electric energy of generation is connected to the grid, power grid needs to have biggish electric loading capacity, utilizes Big power grid to the carrying capacity of periodically fast-changing electric current, can by with the electric energy that cyclic fluctuation changes stabilize with It realizes and utilizes；Electric energy in power grid can be delivered to other electrical equipments, can also drive the pressure in pressure-swing absorption apparatus again Contracting machine and then the gas or liquid compressed, make electric energy obtain reuse.

In pressure-swing absorption process, there is the processes periodically pressurizeed to gas.Therefore, in another implementation In mode, expanding machine drives electric energy caused by motor compressor can be driven to work by motor, completes to gas The pressurized operation of body or liquid, so that electric energy can recycle.

Due to the motor being connected with compressor operation when, overload can be to the appropriate rate of equipment, stability, service life, peace Full property adversely affects, and therefore, in one embodiment, motor can be connected with capacitance group or battery pack, work as electricity When stream fluctuates bigger, capacitance group or battery pack can quickly stabilize electric current and quickly change, and can reinforce motor system The response united to rotation energy needed for quick variation shaft.

The above description is that the embodiments that the mechanical energy generated using expanding machine is converted into electric energy, can also directly utilize Mechanical energy caused by expanding machine.In this embodiment, expanding machine, motor, compressor or pump group are filled at energy regenerating Coaxial drive system or not coaxial drive system can be formed by setting.Composition coaxial drive system is exactly to turn expanding machine Change the mechanical energy to come directly to replenish in the shafting of compressor or pump, while insufficient part provides energy by motor and carries out Supplement, such as motor is connected in biggish power grid, on the one hand by electric energy drive motor running, while motor Shaft is also interlocked with the shaft of expanding machine, realizes that mechanical energy is replenished the effect on motor, this mode simultaneously by expanding machine The mechanical energy that can be directly obtained using expanding machine, also can make the wave of mechanical energy by the collective effect of expanding machine and motor It is dynamic to be stabilized.Coaxial drive system has compact-sized, and overall efficiency is high, whole set equipment expense and operating cost are all relatively low, With preferable economic benefit.

For the process of pressure-variable adsorption, generally can there is high-pressure installation (such as: the adsorption tower of elevated pressures) to Low-voltage device (such as: the adsorption tower of lower pressure) conveying high-pressure gas, so that the pressure reduction of high-pressure tower, and the pressure of lower pressure column Power increases, and is also possible to that the pressure between two gas buffer tanks mutually changes or pressure between adsorption tower and surge tank is mutual Variation.When the energy recycle device using the fluid cushion device and expanding machine in the utility model as main body, Ke Yishi There is the phenomenon that gas temperature decline, this is because energy from when being flowed by high side to low side after expanding machine in existing gas Measuring removal process is to be depressured the expansion process of external output work, and the temperature of the gas of expander outlet can decline, and work as cryogenic gas When entering in the tower that other needs pressurize, adsorption temp can be reduced, and can make the adsorption temp of adsorption tower again lower than desorption Raw temperature, the low adsorbance for being conducive to increase unit adsorbent of temperature when absorption, temperature height when desorption and regeneration are conducive to So that the desorption of adsorbent is more thorough, the dynamic adsorbance of adsorbent is increased.The gas of expander outlet can also be used The cooling capacity that certain temperature is externally exported through heat exchanger is used for other devices.

In addition, gas pressure quickly can also be effectively prevented by adding fluid cushion device before and after expanding machine Power periodicity quick shift；Since excessive and frequent impact load can make the easy dusting of adsorbent, adsorbent is reduced Service life, while also having an adverse effect to the safety of adsorption tower, tired service life, so having used in pressure-swing absorption apparatus It is middle to have used the rapid fluctuations that inhibit high pressure gas with equipment such as control valve, surge tanks, enable to making for adsorbent Extended with the service life, while being also beneficial to the safety and tired service life of adsorption tower.

Based on the operation of above-mentioned energy recycle device, a typical following institute of pressure-swing absorption process in the utility model Show:

One relatively common pressure-variable adsorption industrial process is as described below:

Step 1 is entered the adsorption tower in absorption phase, most of easily absorbed component quilt by the gaseous mixture of upstream supplied materials Adsorbent adsorbs in adsorption tower, and it is absorption phase that most of unsuitable easily absorbed component, which passes through adsorption tower bed,.

Step 2 is depressured what step 1 obtained in the adsorption tower of adsorption saturation, pressure reduction may be with it is another Platform is in the adsorption tower of low-pressure state or vacuum tank, surge tank are pressed, along putting or the processes such as inverse put.During these, The energy that high pressure gas in adsorption saturation adsorption tower can be recycled through energy recycle device recycling is then flowed into low pressure Adsorption tower or vacuum tank, the surge tank of state.It has been completed at the same time recycling and the pressure reduction of normal pressure-variable adsorption of energy.

Step 3, there may be need will be after the resulting decompression in the adsorption tower or vacuum tank, surge tank etc. of step 2 Gas be depressured again or by the gas after decompression by it is certain processing (such as: displacement or again absorption, it is with pressure rinse, Pressurising etc.) after be depressured again.This same process may be to need to take the processing method similar with step 2.This Process may be to be pressed, suitable put or inverse put was waited with another adsorption tower or vacuum tank, surge tank in low-pressure state Journey.During these, the high pressure gas in adsorption saturation adsorption tower recycles the energy that can be recycled through energy recycle device Amount then flows into adsorption tower or vacuum tank, surge tank in low-pressure state.It has been completed at the same time the recycling and normal transformation of energy The pressure reduction of absorption.

Step 4, there may be the similar procedure of step 2 or step 3 is repeated up to adsorption tower drop to it is sufficiently low Pressure.

The adsorption tower that low-pressure state is dropped in step 4 is carried out desorption and regeneration process in a low voltage state by step 5, It may take to vacuumize, purge or vacuumize during this and add the methods of purging or low pressure desorption.

Step 6, there may be need the adsorption tower by low pressure desorption by other adsorption towers in step 3 or steady It presses tank, surge tank to carry out boost pressure process, the process energy regenerating in step 2 or step 3 may be accepted in this process The high pressure gas being depressured afterwards.

Step 7, there may be need will be after the resulting boosting in the adsorption tower or vacuum tank, surge tank etc. of step 6 Gas boosted again or by the gas after boosting by it is certain processing (such as: displacement or again absorption, it is with pressure rinse, Pressurising etc.) after boosted again, may be accepted in these possible boost process in step 2 or step 3 and pass through energy The high pressure gas being depressured after amount recycling.

Step 8, there may be need by the adsorption tower unstripped gas passed through after boosting in step 7 or by adsorption tower Not adsorbed gas after absorption boosts to the pressure close to adsorption step again.

Step 9, preceding 8 processes carry out the continuous continuous operation that moves in circles for single column, for phase between tower and tower Mutually cooperate, alternately move in circles continuous continuous operation.

The processes such as its High Pressure Absorption, decompression energy regenerating, decompression, low pressure desorption move in circles for single column continuous Continuous operation, for cooperating between tower and tower, staggeredly carrying out the continuous continuous operation that moves in circles.

Periodically quickly variation pressure energy recycling during pressure-variable adsorption is separated, is converted to conventional available machinery It can supply to gas-pressurization, save to electric energy consumed by gas pressurized.In contrast to no addition energy recycle device Pressure swing adsorption system, can be recycled routine pressure swing adsorption system in the energy loss due to caused by pressure difference 50%.

In addition, the not adsorbed gas possible pressure in adsorption process after adsorption tower adsorbs is relatively high, or to drop a hint Or do not needed at demand end so high pressure gas can also the gas access amount of high pressure recycle and pressurize couple Device carry out energy regenerating, the gas of the pressure reduction after recovering energy access demand end or is vented again again.

In the utility model, adsorbent employed in adsorption process can be the absorption of any kind of suction-operated Agent is not particularly limited, can be for molecular sieve, active carbon, carbon molecular sieve, activated alumina, carbon fiber etc. and theirs is mixed It closes to load and be layered and load.

The utility model additionally provides a kind of preparation method for aoxidizing dehydrogenation catalyst, includes the following steps:

The surface treatment of Attapulgite carrier: step 1 by weight, takes 10~15 parts of attapulgite, is added molten to silicon In 80~95 parts of glue, 0.5~2h is stirred under the revolving speed of 200~300rpm, then solid is filtered out, after drying, 180~220 1~3h is roasted at DEG C, obtains the attapulgite of area load silica；

The surface of step 2, carrier is modified: by weight, 20~30 parts of attapulgite of area load silica being added Enter into 140~160 parts of alcoholic solution containing silane coupling agent, 2~4h is reacted at 70~75 DEG C, then solid is filtered out, according to It is secondary washed with ethyl alcohol, deionized water after, obtain the carrier of the attapulgite of surface charge；

Step 3, the deposition of active constituent: by weight, by 35~45 parts of carrier of the attapulgite of surface charge It is added containing in 1~5wt% chloroplatinic acid, 0.5~3wt% gold chloride, 80~90 parts of aqueous solution of 4~6wt% copper nitrate, is passed through nitrogen Gas keeps after replacement of oxygen 1~2h, irradiates under xenon lamp, carries out light deposition processing；NaOH solution is added dropwise again keeps copper nitrate heavy It forms sediment, then carries out centrifugal drying, dried object successively obtains catalyst after roasting.

In one embodiment, the solid content of the silica solution is 20~25wt%.

In one embodiment, the silane coupling agent is one of KH550, KH560 or KH570, described Alcoholic solution refers to one of methanol solution, ethanol solution or isobutanol solution；Quality hundred of the silane coupling agent in alcoholic solution Dividing than range is 5~8wt%.

In one embodiment, 200~400W of xenon lamp power, 1~3h of irradiation time.

In one embodiment, the molar ratio of NaOH and copper nitrate is 2:1.

In one embodiment, the roasting in step 3, which refers to, roasts 3h at 400 DEG C.

CO conversion reaction H is used for provided in the utility model₂Catalyst, be mainly copper as activity in The heart, while assisting using platinum and gold as co-catalysis metal, main carrier uses attapulgite；Since attapulgite has Biggish specific surface area, it is impregnated in silica solution can make its surface be covered with one layer of silica, and have can be with for silica Make the surface of attapulgite that negative electrical charge be presented；Attapulgite surface due to having coated silica has negative electrical charge, exists a large amount of Hydroxyl after handling by silane coupling agent, makes its surface by positive charge；Simultaneously as anion in chloroplatinic acid can be with The attapulgite of positive charge can form electrostatic interaction, make chloroplatinic acid ionic adsorption in the surface of carrier, then pass through light deposition After processing, platinum and gold can be effectively improved in the covering uniformity and load capacity of carrier surface；In addition, carrying out surface During the Electrostatic Absorption of chloroplatinic acid, due to be with copper nitrate in the same solution system, can make generate platinum process when, Precipitate to be formed with the copper nitrate on surface and subsequent Kocide SD and uniformly disperse and combine, can make catalyst surface go out compared with High catalytic activity.

Embodiment 1

Coal gas of converter supplied materials first passes through dedusting removal of impurities, enters back into after gas compression unit is pressurized to 0.38MPa by 0.12MPa It is adjusted after being mixed with vapor and enters the progress conversion reaction of multistage insulation shift-converter after temperature is 300 DEG C, using intergrade Water Quench removes exothermic heat of reaction, and 340~480 DEG C of reaction temperature, cooling water goes to waste heat boiler after being heated.After transformed reaction Gas be cooled to again through knockout drum lower than 100 DEG C, gas-liquid separation removing liquid water, then is cooled to after so that vapor is liquefied Through ingredients such as temp.-change adsorptive process removing moisture, sulphur and heavy constituents after 32 DEG C；Gas component mainly contains CO, CO at this time₂、N₂And H₂ And micro O₂And CH₄, this portion gas is sent into pressure-variable adsorption and removes CO₂Device in carry out CO₂With N₂And H₂Separation, It is 0.36MPa in adsorptive pressure, operation temperature removes CO under conditions of being 32 DEG C₂, as the CO for adsorbing phase₂Gas experience absorption Afterwards, then by vacuumizing desorption.Remaining absorbed component composition mixed gas enter pressure-variable adsorption CO and and N₂And H₂Point From in device adsorptive pressure be 0.35MPa, operation temperature be 32 DEG C under conditions of separate CO and N₂And H₂And micro other Component.As absorption phase CO gas experience absorption after, then by vacuumizing desorption after, isolated high-purity CO gas is again Through being pressurized, until pressure carries out catalytic dehydrogenation deoxygenation under conditions of being 0.4MPa, wherein micro hydrogen and oxygen are removed.Through After the CO product gas for high-purity that treated enters intermediate air accumulator, the unstripped gas as synthesizing glycol is synthesized for next step Glycol unit uses.Another part gas mainly contains N as non-adsorbable other components₂And H₂And micro CO, O₂ And CH₄, pressure-variable adsorption is admitted to after going from adsorption tower ejection and mentions hydrogen production device, mainly carries out H here₂With the gas of other components Separation.It is 0.34MPa in adsorptive pressure, operation temperature obtains volume in tower top under conditions of being 32 DEG C and forms 399.9% hydrogen Gas, the hydrogen that pressure-variable adsorption separating-purifying obtains is pressurized to again enter intermediate air accumulator after 3.5MPa after, as synthesizing glycol Unstripped gas for next step synthesizing glycol device use.

1 concrete technology flow process of embodiment is detailed in Fig. 2, and the gas component in each step process is shown in Table 1.

Table 1

Embodiment 2

Blast furnace gas supplied materials first passes through dedusting removal of impurities, then at 200 DEG C, 0.3MPa after cobalt molybdenum system deoxidier deoxidation, Enter back into gas compression unit be pressurized to after 0.9MPa mixed with vapor after adjust and enter multistage insulation after temperature is 300 DEG C and become Change reactor carry out conversion reaction, using intergrade water Quench remove exothermic heat of reaction, 340~480 DEG C of reaction temperature, cooling water quilt Waste heat boiler is gone to after heating.Gas after transformed reaction is cooled to through knockout drum lower than 100 DEG C again, makes vapor liquid Gas-liquid separation removes liquid water after change.Gas component mainly contains CO, CO at this time₂、N₂And H₂And micro O₂And CH₄, by this Portion gas is sent into low temperature washing device for methanol after being cooled to -40 DEG C again and carries out removing CO₂And micro sulphur, it is in pressure 0.9MPa, operation temperature remove CO under conditions of being -50 DEG C₂And after micro sulphur, gas after processing is warming up to 32 again The ingredients such as moisture and heavy constituent are removed through temp.-change adsorptive process after DEG C；Then gas enters pressure-variable adsorption CO and and N₂And H₂Separation In device adsorptive pressure be 0.8MPa, operation temperature be 32 DEG C under conditions of separate CO and N₂And H₂And other micro groups Point.As absorption phase CO gas experience absorption after, then by vacuumizing desorption after, isolated high-purity CO gas passes through again Pressurization removes wherein micro hydrogen and oxygen until pressure carries out catalytic dehydrogenation deoxygenation under conditions of being 0.45MPa.Through After the CO product gas for high-purity that treated enters intermediate air accumulator, the unstripped gas as synthesizing glycol is synthesized for next step Glycol unit uses.Another part gas mainly contains N as non-adsorbable other components₂And H₂And micro CO, O₂ And CH₄, pressure-variable adsorption is admitted to after going from adsorption tower ejection and mentions hydrogen production device, mainly carries out H here₂With the gas of other components Separation.It is 0.8MPa in adsorptive pressure, operation temperature obtains volume in tower top under conditions of being 32 DEG C and forms 399.9% hydrogen, The hydrogen that pressure-variable adsorption separating-purifying obtains is pressurized to again enter intermediate air accumulator after 3MPa after, the raw material as synthesizing glycol Gas is used for next step synthesizing glycol device.

H is prepared under the technique of the present embodiment and reaction process₂/ CO unstripped gas has not only obtained the raw material of synthesizing glycol Gas has also recycled technical grade nitrogen, and a small amount of methane contained is carried out catalysis burning instead in the high temperature workshop section of blast furnace gas It should handle, environmental protection index is more secure.

H is prepared under the technique of the present embodiment and reaction process₂Mainly consideration with low-temp methanol washes absorption process to/CO unstripped gas Remove CO₂Instead of removing CO using pressure swing adsorption method in the pressure-changeable adsorption decarbonization device mentioned in embodiment 1₂。

2 concrete technology flow process of embodiment is detailed in Fig. 3, and the gas component in each step process is shown in Table 2.

Table 2

3 the present embodiment of embodiment is used to illustrate the energy recovery process in two tower pressure-variable adsorptions

Also contain micro N in certain exhaust gas₂、CO、CO₂、CH₄, the impurity such as Ar, need to be arranged to reach product hydrogen demands Hydrogen separation unit carries out separating-purifying.Since the operating pressure of upstream device is higher, the pressure-variable adsorption separator of H2 is caused The raw gas pressure of entrance is higher, while needing to complete the H after separation₂Need to be pressurized to 4.2 MPa (G).

Unstripped gas condition:

Flow: 2000Nm³/ h(butt)

Pressure: 2.2MPa (G)

Temperature: 32 DEG C of ≈

Total H₂O、O₂、NH₃、CH₃OH, chlorine, phosphorus, arsenic, fluorine, HCN :≤0.1ppm

Through being equipped with H₂The Pressure Swing Adsorption device for separating Special adsorbent carries out isolation of purified, and separating step includes: to inhale Attached, drop pressure inversely bleeds off pressure, vacuumizes, boost pressure, final pressurising.In the step of including pressure change: pressing, is inverse The device that energy regenerating and pressurization coupling are used in bleeding off pressure, finally boost has recycled energy, has been completed at the same time H₂Specially point From purification.

Energy regenerating and the device of pressurization coupling be screw expander, compressor, motor unit at system and its is auxiliary It helps the capacitance group of effect, adjust valve group, flywheel, multiple surge tanks, further include the complication systems such as gear and control system. In pressurized H₂Before entering in energy recycle device and the surge tank that a constant volume is added after energy recycle device is left, is come Stabilize pressurized H₂Pressure and flow fluctuation, keep its basicly stable.

The device provided in the present embodiment is as shown in Figure 5 and Figure 6, wherein the exhaust pipe of adsorption tower 1A is connected to expanding machine Level-one 2, the discharge directions of the level-one 2 of expanding machine are connected with adsorption tower 1B again, in the inlet and outlet of the level-one 2 of expanding machine On the pipeline of side, it is connected separately with surge tank 13,14, the shaft of the level-one 2 of expanding machine is connected with motor 4 again, motor 4 It is connected again with compressor 3, for being also equipped with respectively by inlet for pressurised gas in the inlet and outlet of compressor 3 to gas pressurized Surge tank 11 and by compressed gas export surge tank 12, capacitance group 10 is also connected on motor 2.

Operating process below in conjunction with the device runs it and is further described:

The adsorption tower 1A(hereinafter referred to as A tower in the period of (0 ~ 3min)) process adsorbed, valve A5A1 opens, Unstripped gas enters the adsorption tower A tower of state to be adsorbed by unstripped gas vacuum tank (18) and regulating valve E4；The unadsorbed gas of tower top Body is used as product gas for other devices by product gas vacuum tank (19) and regulating valve E3.Adsorption tower 1B(hereinafter referred to as B Tower) process that is vacuumized, valve B6 opens, vacuumized through taking out air surge tank (5) to B tower by reciprocating pump (6).Energy Amount recyclable device does not have gas to pass through, and does not recover energy and supplies compressor (3) progress gas compression.

The process that A tower and B tower are pressed is carried out in the period of (3 ~ 4min), valve A2B3E2 is opened, and utilizes A tower In high pressure gas boost to B tower, firstly, in the moment that valve A2B3E2 is opened, pressure in pipeline, expanding machine (3) into The pressure difference of outlet, changes in flow rate are all very big, so will cause bigger shock loading, excessive shock loading will affect equipment Steady, safe operation, will affect service life of equipment.So by regulating valve E5E10, to adjust the inlet and outlet of expanding machine 3 Pressure difference, flow reduce the aperture of regulating valve E5E10, suppress to corresponding adsorption tower in the moment that valve A2B3 E2 is opened Pressure, to reduce influence of the impact load to expanding machine.Also by expanding machine inlet/outlet pipeline be connected surge tank (13) (14) come It is buffered, when pressure is higher than the pressure of valve E6E7 setting in the pipeline being connected with surge tank, valve E6E7 is opened, buffering Tank is connected with pipeline, and gas distribution is made to enter surge tank, reduces the shadow for entering the amount reduction impact load of the gas of expanding machine It rings, strives for the required time for the movement of expanding machine regulating mechanism, so that the slide valve of adjusting control mechanism movement screw expander, Adjust the outer pressure ratio and flow of the expanding machine inlet and outlet after can be adapted to valve opening by the flow, inner pressure ratio, interior volume specific ratio of expanding machine. The pressure energy band moving axis acted on expanding machine simultaneously rotates, and the mechanical energy of axis is converted into, due to the impact load formed when valve opening Easily making axis revolving speed is more than the revolving speed that needs of setting, and it is complete that the change of axis revolving speed is unfavorable for the same common driving compressor of motor formation resultant force The compression process of pairs of another gas increases axis by increasing the flywheel of certain size and certain mass distribution in shaft Rotary inertia is conducive to the stabilization of the revolving speed of shaft fixed so that shaft says that the acceleration obtained reduces under identical torque Need revolving speed.The shaft of expanding machine is connected with motor (4), can drive motor rotation, but since expanding machine institute is defeated Mechanical energy revolving speed out can lead to cyclically-varying due to the frequent change procedure of pressure-variable adsorption, will lead to the fortune of motor Row is unstable, and therefore, electric current needed for motor needs to access overall grid, using big power grid to periodically fast-changing The carrying capacity of electric current, application control device smoothly drive to complete motor.Under Impact Load, power grid is to electronic The flow of electric current of machine input may quickly reduce, or even cause the change of the conveying direction of electric current, thus by motor and Capacitance group (10) connects, and to stabilize the quick variation of the flow of caused electric current under Impact Load, can reinforce electronic Machine system reduces the impact to power grid to the responding ability of rotation energy needed for quick variation shaft.With the lengthening of runing time, Since the gas in A tower gradually flows to B tower, A pressure tower is gradually decreased, and B pressure tower gradually rises, and the pressure difference between two towers is gradually Reduce, the pressure difference of gas is gradually reduced between expanding machine inlet and outlet, and flow is also gradually reduced, what this process gradually changed.It adjusts The aperture of big regulating valve E5E10, reduces the drag losses at valve.As expanding machine import and export line pressure gradually changes, Gas tapers to outflow surge tank by inflow surge tank, when pressure is set lower than valve E6E7 in the pipeline being connected with surge tank When fixed pressure, valve E6E7 is closed, and surge tank is no longer connected to pipeline.Since gas compressed needs basicly stable pressure Power and flow, it means that the needs of shaft power needed for the gas of compression are basicly stable, so gas compressed is in compressor Inlet and outlet have all accessed surge tank to cope with the fluctuation of possible pressure and flow, with the variation of time, expanding machine inlet and outlet Between the pressure difference of gas be gradually reduced, flow is also gradually reduced, so the shaft power that expanding machine is exported also is gradually becoming smaller, then The shaft power for needing motor to be exported becomes larger, then the electric current of power grid input is needed to adjust by control system and be become larger Shaft power needed for carrying out completion gas compressed.Electric current needed for motor needs to access overall grid, utilizes big power grid To the carrying capacity of periodically fast-changing electric current, application control device smoothly drives to complete motor.Pass through simultaneously The slide valve of adjusting control mechanism adjusting screw rod expanding machine, adjusting to expand by the flow, inner pressure ratio, interior volume specific ratio of expanding machine The higher efficiency of the holding of machine.

Since energy recovery process is the expansion process for being depressured external output work, the temperature of the gas of expander outlet can under Drop, cooling extent are determined that the gas of expander outlet is externally exported through heat exchanger (20) (21) by the pressure difference of expanding machine import and export The cooling capacity of certain temperature is used for other devices.The gas of expander outlet enters B tower, and the process of boost pressure is carried out to B tower, Gas temperature after certain cooling capacity is recycled in heat exchange is lower than the gas temperature at expander inlet end, and the entrance of cryogenic gas is so that B The temperature of tower reduces.For B tower, equally existed in the Plenum Process of next step similar cryogenic gas entrance so that The process that the temperature of B tower reduces, can make B tower in the step of being adsorbed in next step, the adsorption temp of B tower can reduce, meeting So that the adsorption temp of adsorption tower is lower than the temperature of desorption and regeneration, the low suction for being conducive to increase unit adsorbent of temperature when absorption Attached amount, what temperature height when desorption and regeneration advantageously allowed the desorption of adsorbent more thoroughly increases the Dynamic Adsorption of adsorbent Amount.Simultaneously because gas has carried out energy regenerating by expanding machine, the boost or depressurization process of adsorption tower can be made to tend to slowly, Compared to the pressure-swing absorption apparatus for not using energy regenerating, reduce the gas in pressure equalizing to the impact lotus of adsorption tower It carries.Excessive and frequent impact load can make the easy dusting of adsorbent, reduce the service life of adsorbent, while also to adsorption tower Safety, tired service life has an adverse effect.Energy regenerating dress has been used in pressure-swing absorption apparatus so having used Meeting is set so that the service life of adsorbent extends, while being also beneficial to the safety and tired service life of adsorption tower.

A tower carries out inverse put in the period of (4 ~ 5min), and B tower carries out Plenum Process.Valve A4E13 is opened, in A tower High pressure gas is after energy recycling system has recycled pressure energy and cooling capacity through reverse gas surge tank (7) and inverse put air compressor (8) After go to other burners.It is similar with the function situation of energy recycling system in pressure equalizing, it is formed in the moment of valve opening Impact load is worked as a buffer and is delayed by adjusting valve group E6E8E9, surge tank (13) (15) (16), flywheel, capacitance group (10) The access of solution and big power grid, the adjusting of expanding machine slide valve can also play certain buffer function to impact load.Equally Similar with the function situation of energy recycling system in pressure equalizing, with the lengthening of runing time, in A tower, the pressure of gas is gradually It reduces, the pressure difference of gas is gradually reduced between expanding machine inlet and outlet, and flow is also gradually reduced, so the shaft work that expanding machine is exported Rate is also gradually becoming smaller, then the shaft power for needing motor to be exported becomes larger, then the electric current needs of power grid input pass through control System processed adjusting becomes larger carry out completion gas compressed needed for shaft power.Electric current needed for motor needs to access whole Power grid, using big power grid to the carrying capacity of periodically fast-changing electric current, application control device is flat to complete motor Steady driving, capacitance group are output and input smoothly to drive motor and are also contributed by electric current.Simultaneously by adjusting control The slide valve of mechanism adjusting screw rod expanding machine processed, so that the flow of expanding machine, inner pressure ratio, interior volume specific ratio are enabled suitable for swollen after valve opening The outer pressure ratio and flow of swollen machine inlet and outlet, make expanding machine keep higher efficiency.Equally pass through the heat exchanger at expander outlet Externally the cooling capacity of output certain temperature is used for other devices.The function situation class of energy recycling system in same and pressure equalizing Seemingly, because joined energy recycling system during pressure change is excessive, so that the service life of adsorbent extends, simultaneously It is also beneficial to the safety and tired service life of adsorption tower.Valve E1E2B3 is opened, the high pressure in product gas vacuum tank (19) Gas carries out pressurising to B tower after energy recycling system has recycled pressure energy and cooling capacity, is increased to B pressure tower close to absorption step Rapid pressure.Energy recycling system is to input current in the coping style of the shock loading of valve opening, power grid in this course Change externally provided to stable driving, by heat exchanger cooling capacity, slide valve to expanding machine flow, inner pressure ratio, interior volume specific ratio tune It saves similar along journey is let off with A tower.Gas temperature after certain cooling capacity is recycled in heat exchange is lower than the gas at expander inlet end Temperature, the entrance of cryogenic gas is so that the temperature of B tower reduces.

The process that B tower is vacuumized in the period of (5 ~ 8min), valve A6 open, by reciprocating pump (6) to A tower into Row vacuumizes.B tower is in adsorbed state, and unstripped gas enters state to be adsorbed by unstripped gas vacuum tank (18) and regulating valve E4 Adsorption tower B tower；Tower top unabsorbed gases supply other devices as product gas by product gas vacuum tank (19) and regulating valve E3 It uses.B tower is since in boost pressure and Plenum Process before, the temperature of the gas after energy regenerating of receiving is lower than The gas temperature at expander inlet end.Meeting so that the adsorption temp of B tower can reduce, the B absorption the step of in, adsorption tower can be made Adsorption temp be lower than and vacuumize the temperature of desorption and regeneration, the low absorption for being conducive to increase unit adsorbent of temperature when absorption Amount, temperature height when desorption and regeneration advantageously allow the desorption of adsorbent more thoroughly, increase the dynamic adsorbance of adsorbent. Energy recycle device does not have gas to pass through in this period, does not recover energy and supplies compressor (3) progress gas compression.

The process that B tower and A tower are pressed is carried out in the period of (8 ~ 9min), valve B2A3 is opened, using in B tower High pressure gas boost to A tower.Its process is similar with the process pressed of (3 ~ 4min) section, between A tower and B tower mutually Cooperation, alternately move in circles continuous continuous operation.

A tower carries out Plenum Process in the period of (9 ~ 10min), and B tower carries out inverse put process.Valve E1E2B3, product High pressure gas in gas vacuum tank (19) carries out pressurising to A tower after energy recycling system has recycled pressure energy and cooling capacity, makes A tower Pressure rise is to the pressure close to adsorption step.Valve B4E13 is opened, and the high pressure gas in A tower is returned by energy recycling system Other burners are gone to after reverse gas surge tank (7) and inverse put air compressor (8) after having received pressure energy and cooling capacity.Its process and A tower carries out inverse put in (4 ~ 5min) section, and B tower progress Plenum Process is similar, cooperates between A tower and B tower, alternately Move in circles continuous continuous operation.

So far, adsorption tower completes a complete adsorption-regeneration cycles process, and carries out for next cyclic process Prepare.The operating process of B tower is identical with tower A, and the operation of the alternately each step of each adsorption tower follows single column The reciprocal continuous continuous operation of ring, for cooperating between tower and tower, alternately move in circles continuous continuous operation.

Pressure-variable adsorption is separated into H by pressure-variable adsorption₂During periodically quickly variation pressure energy recycling, be converted to often Available mechanical energy supply is advised to H₂Pressure process and the cooling capacity externally exported, save to H₂Electric energy consumed by pressurizeing.It is right Than can be recycled in routine pressure swing adsorption system since pressure difference causes in no pressure swing adsorption system that energy recycle device is added Energy loss 46%.

3 liang of tower pressure swing adsorption purge H of table₂Circulate operation step time-scale

4 the present embodiment of embodiment is used to illustrate the energy recovery process in three tower pressure-variable adsorptions

Also contain micro N in certain exhaust gas₂、CO、CO₂、CH₄, the impurity such as Ar, need to be arranged to reach product hydrogen demands Hydrogen separation unit carries out separating-purifying.Since the operating pressure of upstream device is higher, the pressure-variable adsorption separator of H2 is caused The raw gas pressure of entrance is higher, while needing to complete the H after separation₂Need to be pressurized to 4.2 MPa (G).

Unstripped gas condition:

Flow: 2000Nm³/ h(butt)

Pressure: 2.2MPa (G)

Temperature: 32 DEG C of ≈

Total H₂O、O₂、NH₃、CH₃OH, chlorine, phosphorus, arsenic, fluorine, HCN :≤0.1ppm

Through being equipped with H₂The Pressure Swing Adsorption device for separating Special adsorbent carries out isolation of purified, and separating step includes: to inhale Attached, drop pressure inversely bleeds off pressure, vacuumizes, boost pressure, final boosting.In the step of including pressure change: pressing, is inverse The device that energy regenerating and pressurization coupling are used in bleeding off pressure, finally boost has recycled energy, has been completed at the same time H₂Specially point From purification.Energy regenerating and the device of pressurization coupling are the system of turbo-expander, compressor, motor compressor composition, and The capacitance group of its booster action adjusts valve group, flywheel, multiple surge tanks, further includes the complicated system such as gearbox and control system System.In pressurized H₂A constant volume is added in entering energy recycle device before compressor and after leaving energy recycle device Long-pending surge tank, to stabilize pressurized H₂Pressure and flow fluctuation, keep its basicly stable.

As shown in Figure 7.

Energy regenerating mistake in each operating procedure of this pressure-variable adsorption and energy regenerating and the device of pressurization coupling Journey has similar process.For pressure, adjusting are swollen in the moment pipeline of valve opening in operating procedure conversion process in operating process All very greatly, so will cause bigger shock loading, excessive shock loading be will affect for the pressure difference variation of swollen machine entrance end Steady, the safe operation of equipment, the service life that will affect equipment.So by regulating valve E2E5, to adjust expanding machine inlet and outlet Pressure difference, flow, valve open moment, reduce regulating valve E2E5 aperture, build the pressure to corresponding adsorption tower, to subtract Few influence of the impact load to expanding machine.Also by expanding machine inlet/outlet pipeline be connected surge tank (13) (14) (15) (16) come It is buffered, when pressure is higher than the pressure of valve E6E7E8E9 setting in the pipeline being connected with surge tank, valve E6E7E8E9 It opens, surge tank is connected with pipeline, and gas distribution is made to enter surge tank, reduces the amount reduction impact for entering the gas of expanding machine The influence of load strives for the required time for the movement of expanding machine regulating mechanism, so that adjusting control mechanism acts turbine expansion The deflection angle of the inlet vanes of machine or the aperture of adjustable nozzle adjust and can be adapted to valve opening by flow, the pressure difference of expanding machine The pressure difference and flow of expanding machine import and export afterwards.The pressure energy band moving axis acted on expanding machine simultaneously rotates, and is converted into axis Mechanical energy, since the impact load easily band moving axis revolving speed formed when valve opening accelerates, the change of axis revolving speed is unfavorable for same motor and is formed The common driving compressor of resultant force completes the compression process of another gas, by increasing certain size and certain mass point in shaft The flywheel of cloth increases the rotary inertia of axis, so that shaft says that the acceleration obtained reduces under identical torque.Needed for motor Electric current need to access overall grid, using big power grid to the carrying capacity of periodically fast-changing electric current, application control Device smoothly drives to complete motor.Under Impact Load, power grid may to the flow for the electric current that motor inputs Quickly reduce, or even cause the change of the conveying direction of electric current, so being connected by motor and capacitance group, is being impacted to stabilize The quick variation of the flow of caused electric current under load action can reinforce electric motor system to rotation needed for quick variation shaft The responding ability of energy reduces the impact to power grid.With the lengthening of runing time, due to the gas in high-pressure tower gradually flow to it is low Pressure tower or vacuum tank, high pressure pressure tower gradually decrease, and low pressure pressure tower gradually rises, and the pressure difference between two towers is gradually reduced, swollen The pressure difference of gas is gradually reduced between swollen machine inlet and outlet, and flow is also gradually reduced, what this process gradually changed.Tune up regulating valve The aperture of E2E5 reduces the drag losses at valve.As expanding machine import and export line pressure gradually changes, gas is by flowing into Surge tank tapers to outflow surge tank, when pressure is lower than set by valve E6E7E8E9 in the pipeline being connected with surge tank When pressure, valve E6E7E8E9 is closed, and surge tank is no longer connected to pipeline.Since gas compressed needs basicly stable pressure Power and flow, it means that the needs of shaft power needed for the gas of compression are basicly stable, so gas compressed is in compressor Inlet and outlet have all accessed surge tank to cope with the fluctuation of possible pressure and flow, with the variation of time, expanding machine inlet and outlet Between the pressure difference of gas be gradually reduced, flow is also gradually reduced, so the shaft power that expanding machine is exported also is gradually becoming smaller, then The shaft power for needing motor to be exported becomes larger, then the electric current of power grid input is needed to adjust by control system and be become larger Shaft power needed for carrying out completion gas compressed.Electric current needed for motor needs to access overall grid, utilizes big power grid To the carrying capacity of periodically fast-changing electric current, application control device smoothly drives to complete motor.Pass through simultaneously Adjusting control mechanism adjusts the deflection angle of the inlet vanes of turbo-expander or the aperture of adjustable nozzle, and adjusting passes through expansion Flow, the pressure difference of machine make the higher efficiency of the holding of expanding machine.Since energy recovery process is the swollen of the external output work of decompression The temperature of swollen process, the gas of expander outlet can decline, and cooling extent determines that expanding machine goes out by the pressure difference that expanding machine is imported and exported The cooling capacity that the gas of mouth externally exports certain temperature through heat exchanger is used for other devices.The gas of expander outlet enters low pressure Tower, to the process that lower pressure column boosts, the gas temperature after certain cooling capacity is recycled in heat exchange is lower than the gas at expander inlet end Temperature, the entrance of cryogenic gas is so that the temperature of lower pressure column reduces.Boosting for lower pressure column, in following step Journey equally exists the entrance of similar cryogenic gas so that the process that the temperature of lower pressure column reduces, can make lower pressure column boost After in the step of being adsorbed, the adsorption temp of lower pressure column can reduce, and the adsorption temp of adsorption tower can be made lower than desorption Regenerated temperature, the low adsorbance for being conducive to increase unit adsorbent of temperature when absorption, temperature when desorption and regeneration are high advantageous The dynamic adsorbance of adsorbent is more thoroughly increased in the desorption for making adsorbent.Simultaneously because gas is carried out by expanding machine Energy regenerating can make the boost or depressurization process of adsorption tower tend to slowly, compared to the transformation for not using energy regenerating Adsorbent equipment reduces the gas in pressure equalizing to the impact load of adsorption tower.Excessive and frequent impact load can make The easy dusting of adsorbent, reduces the service life of adsorbent, while also unfavorable to the safety of adsorption tower, tired service life generation It influences.So the service life for having used energy recycle device that can make adsorbent in pressure-swing absorption apparatus has been used to extend, It is also beneficial to the safety and tired service life of adsorption tower simultaneously.

In simple terms, by the way that the buffering of a constant volume is added in pressure-variable adsorption and energy regenerating and the device of pressurization coupling Tank stabilizes the pressure of gas in pipelines or the fluctuation of flow with valve group is adjusted, and first recycles pressure-variable adsorption by turbo-expander The energy of middle gas is converted into the mechanical energy of axis.What addition certain size and certain mass were distributed in energy recycle device flies It takes turns to increase the rotary inertia of axis, to stabilize the rotation energy for periodically quickly changing shaft.Then again control system according to system The gross energy needed determines the power output needed by motor compressor, control motor power output, then is mentioned by motor compressor or electrodynamic pump Required remaining energy is supplemented for energy to H₂Complete pressurization.Being connected with capacitance group for motor, works as current wave When moving bigger, battery pack can quickly stabilize electric current and quickly change, and can reinforce electric motor system and turn to quick variation The response of rotation energy needed for axis.Electric current needed for motor needs to access overall grid, using big power grid to periodically quick The carrying capacity of the electric current of variation, application control device smoothly drive to complete motor.To which pressure-variable adsorption is separated H₂ During periodically quickly variation pressure energy recycling, be converted to conventional available mechanical energy supply to H₂Pressure process, section It has saved to H₂Electric energy consumed by pressurizeing.In contrast to no pressure swing adsorption system that energy recycle device is added, can be recycled normal Advise 46% of the energy loss due to caused by pressure difference in pressure swing adsorption system.And for pressure-swing absorption process, it is inhaled according to three tower transformations Attached purification H2 circulate operation step time-scale (subordinate list 1), the operation of the alternately above each step of each adsorption tower, for list Tower carries out the continuous continuous operation that moves in circles, and for cooperating between tower and tower, alternately moving in circles constantly connects Reforwarding row.

Reverse gas and pumping air lead to the exhaust gas torch pipe network of plant area as exhaust gas, pass through H₂Adsorption separation device obtains pure The H2 of degree >=99.9% is 1300 Nm³/ h, remaining CO be about 0.03%, CO₂About 0.03%, N₂About 0.03%, Ar+CH₄About It is 0.01%；Reverse gas and pumping 700 Nm of air³/ h, wherein CO be about 31.94%, CO₂About 28.59%, N₂About 29.22%, H₂ About 9.37%, CH₄About 0.88%.

Pressure-variable adsorption separates H₂Process, this pressure-variable adsorption process is illustrated by taking A tower as an example:

(a) adsorb (0 ~ 2min): under 2.2MPa pressure, valve A4 opening unstripped gas enters fixed bed and is adsorbed, Absorption forward position just stops absorption before not reaching bed exit end, makes to retain a Duan Xinxian between absorption forward position and bed outlet Bed, the resulting H of tower top₂It is discharged as product gas by the valve A1 of the opening of tower top.Adsorptive pressure comes close to unstripped gas Expect pressure.

(b) adsorb (2 ~ 3min): the outlet of A column overhead is connected by A tower while absorption with the B tower after rising, The part H obtained with tower top₂Pressurising step is carried out to B tower, this step need to be recycled by the device of energy regenerating and pressurization coupling Energy, valve A1A4 are opened, and A column overhead valve A2, B tower tower bottom valve B3, E3E6E7 valve is opened, when gas in the connected tank of E6 Pressure when being lower than 1.9MPa E6 close, the E7 closing when the pressure of gas in the connect tank of E7 is lower than 1.4MPa.Adjust valve group E2, E5 are can to reduce to adjust pressure in pipeline and gas flow becomes larger or becomes smaller so that turbo-expander (2) The fluctuation of operation.The connected surge tank of E6E7 valve and adjusting valve group E2, E5 can be buffered in the moment that valve has just been opened by saturating The flow and pressure difference of the gas of flat turbo-expander, can reduce the momentary output of turbo-expander.

(c) drop (3 ~ 4min): by A tower in vacuum state C tower be connected progress pressure step, this walk need through The device for crossing energy regenerating and pressurization coupling has recycled energy, and A column overhead valve A2, C tower tower bottom valve C3, E3E6E9 valve is beaten It opens, when the pressure of gas in the connected tank of E6 is lower than 1.9MPa, E6 is closed, when the pressure of gas in the connected tank of E9 is lower than 0.4MPa When E7 close.It adjusts valve group E2, E5 and is to adjust pressure in pipeline and gas flow becomes larger or becomes smaller, can reduce So that the fluctuation of turbo-expander operation.The moment that the connected surge tank of E6E9 valve and adjusting valve group E2, E5 have just been opened in valve The flow and pressure difference that the gas by turbine turbo-expander can be buffered, can reduce the momentary output of turbo-expander.It is right It is one section of pressure reduction for tower A, is one section of boost process for tower C.The pressure of A tower is slightly above reset pressure after pressing The purity of half (1.1MPa), the purity for body of calming the anger and the product gas flowed out from tower top is essentially identical.

(d) inverse put (4 ~ 5min): by A tower in close to normal pressure state reverse gas surge tank be connected progress inverse put step Suddenly, inverse put circuit is walked at this simultaneously need to recycle energy by the device of energy regenerating and pressurization coupling, A tower tower bottom valve A3, E1E4E8E9 valve is opened, and when the pressure of gas in the connected tank of E8 is lower than 0.9MPa, E8 is closed, when gas in the connected tank of E9 E9 is closed when pressure is lower than 0.4MPa.Adjusting valve group E2, E5 is to adjust pressure in pipeline and gas flow and become larger Or become smaller, the fluctuation so that turbo-expander operation can be reduced.The connected surge tank of E8E9 valve and adjusting valve group E2, E5 are in valve The moment that door has just been opened can buffer the flow and pressure difference of the gas by turbine turbo-expander, can reduce turbo-expander Momentary output.After drop pressure process, the impurity forward position in adsorbent bed has reached the outlet port of adsorption tower.This When, adsorption column pressure is down to close to normal pressure (0.11MPa) against absorption direction.In the process, it is adsorbed in adsorption tower Impurity starts largely to desorb from adsorbent.Inversely gas is bled off pressure after reverse gas surge tank (7) and inverse put air compressor (8) Go to other burners.

(e) it vacuumizes (5 ~ 6min): after inverse put step, to make adsorbent obtain more thoroughly regenerating, to absorption Tower evacuates, and desorbs adsorbent thoroughly.The A5 valve for opening A tower bottom, inversely vacuumizes bed with vacuum pump (6), tower Interior pressure extremely -0.09MPa.

(f) it rises (6 ~ 7min): the A tower in vacuum state is connected progress with the B tower terminated in adsorbed state Press step.It is one section of Plenum Process for tower A, is one section of pressure reduction for tower B.A tower tower bottom valve A3, B column overhead Valve B2, E3E6E9 valve is opened, this step need to recycle energy by the device of energy regenerating and pressurization coupling, and process is similar In the process that (c) drops, only A tower becomes the lower pressure column by boost pressure for receiving gas.The pressure of A tower after pressing The slightly below half (0.9MPa) of adsorption step pressure, the purity of the purity for body of calming the anger and the product gas flowed out from B column overhead It is essentially identical.

(g) vacant (7 ~ 8min): A column overhead, tower bottom valve are all closed, and do not have gas disengaging in A tower, and A tower, which is in, to be waited State.

(h) pressurising (8 ~ 9min): by A tower and the C column overhead after rising export be mutually used in conjunction part H2 to A tower into Row pressurising step increases A tower internal pressure, close to adsorptive pressure (2.1MPa).A tower tower bottom valve A3, C column overhead valve C2, E3E6E7 valve are opened, this step need to be analogous to (b) by the process that the device of energy regenerating and pressurization coupling has recycled energy The process of absorption, only A tower becomes the lower pressure column being pressurized for receiving gas.

So far, adsorption tower completes a complete adsorption-regeneration cycles process, and carries out for next cyclic process Prepare.The operating process of other three towers is identical with tower A, the operation of the alternately above each step of each adsorption tower, right The continuous continuous operation that moves in circles is carried out in single column, for cooperating, alternately being moved in circles constantly between tower and tower Continuous operation.

Its specific ring operating procedure and operating time and timing are referring to table 1, the therebetween control of each valve opening state of each tower System and operation are referring to table 4.According to time-scale (table 4) and valve opening control table (table 5) it is known that energy recycling system is in Continuous duty is alternately present for pressure, inverse put, Plenum Process, and alternately move in circles continuous continuous operation, energy Recovery system is continuously run, and recycles the energy in this 3 operating procedures, so that energy recycling system avoids zero load, Be conducive to machine to safely and steadily run, avoid the loss of the adverse effect and energy to machine.

4 three tower pressure swing adsorption purge H of table₂Circulate operation step time-scale

Each tower valve opening control table of table 5

Above embodiments do not constitute the limitation to utility model.

Claims (10)

1.H₂The process units of/CO unstripped gas characterized by comprising

Shift-converter is obtained for coal gas to be carried out Partial Transformation reaction containing CO, H₂And N₂Reaction gas；

First pressure-swing absorption apparatus, is connected to shift-converter, for the CO in obtained reaction gas to be passed through pressure-variable adsorption Method is isolated；

Second pressure-swing absorption apparatus is connected to the first pressure-swing absorption apparatus, for carrying out pressure-variable adsorption to except the gaseous mixture after CO Separate H₂And N₂。

2. H according to claim 1₂The process units of/CO unstripped gas, which is characterized in that further include: it is used for preparing ethylene glycol Reactor, be connected to the first pressure-swing absorption apparatus CO outlet and the second pressure-swing absorption apparatus H₂Outlet is closed for reacting At ethylene glycol.

3. H according to claim 1₂The process units of/CO unstripped gas, which is characterized in that the shift-converter connection In the gas feed for including blast furnace gas or coal gas of converter.

4. H according to claim 1₂The process units of/CO unstripped gas, which is characterized in that the coal of the shift-converter Gas import is also connect with the first exclusion device.

5. H according to claim 3₂The process units of/CO unstripped gas, which is characterized in that contain blast furnace gas or converter The access port of coke-stove gas or periodic off-gases is also connected in gas inlet.

6. H according to claim 4₂The process units of/CO unstripped gas, which is characterized in that the first exclusion device packet It includes dust-extraction unit, dephosphorization apparatus, arsenic removing apparatus, dehydration device, device for deoxidizing, desulfurizer or removes CH₄One in device Or several combination.

7. H according to claim 1₂The process units of/CO unstripped gas, which is characterized in that the first pressure-swing absorption apparatus passes through Second exclusion device is connected to shift-converter；Second exclusion device includes removing CO₂Device.

8. H according to claim 7₂The process units of/CO unstripped gas, which is characterized in that described removes CO₂Device is to inhale Receipts method removes CO₂Device or absorption method remove CO₂Device.

9. H according to claim 8₂The process units of/CO unstripped gas, which is characterized in that on the first pressure-swing absorption apparatus The outlet CO is connected to third exclusion device.

10. H according to claim 9₂The process units of/CO unstripped gas, which is characterized in that the third exclusion device Including dehydrogenation deaerating plant.