CN109694039A

CN109694039A - A kind of reforming hydrogen-preparation reactor, hydrogen manufacturing conversion furnace and method for preparing hydrogen by reforming

Info

Publication number: CN109694039A
Application number: CN201710985866.6A
Authority: CN
Inventors: 张旭; 戴文松
Original assignee: Sinopec Engineering Inc; Sinopec Engineering Group Co Ltd
Current assignee: Sinopec Engineering Inc; Sinopec Engineering Group Co Ltd
Priority date: 2017-10-20
Filing date: 2017-10-20
Publication date: 2019-04-30
Anticipated expiration: 2037-10-20
Also published as: CN109694039B

Abstract

This disclosure relates to a kind of reforming hydrogen-preparation reactor, hydrogen manufacturing conversion furnace and method for preparing hydrogen by reforming.The reforming hydrogen-preparation reactor uses micro- catalysis reaction plate, active component needed for load has hydrogen production reaction on reaction plate, reduce catalytically-active metals dosage and catalyst is not easy carbon distribution inactivation, shortens the distance that reaction gas diffuses to catalytic active center, resistance to mass tranfer and reactor pressure decrease are reduced, hydrogen production reaction conversion ratio is improved；Reaction gas is flowed by center outward in the reactor, and flow area, which is gradually increased, reacts plate temperature gradually rises, and is increased advantageous as volume and the promotion of the hydrogen production reaction conversion ratio of the endothermic reaction；The reforming hydrogen-preparation reactor use scope is wide, and the boiler tube as hydrogen manufacturing conversion furnace can be adapted for different types of reburner.Low using the hydrogen production process boiler tube pressure drop of the reformation hydrogen production reburner, per volume of catalyst in boiler tube product space-time yield height, unstripped gas processing capacity energy high conversion rate, can satisfy hydrogen production reaction requirement.

Description

A kind of reforming hydrogen-preparation reactor, hydrogen manufacturing conversion furnace and method for preparing hydrogen by reforming

Technical field

This disclosure relates to reformation hydrogen production field, and in particular, to a kind of reforming hydrogen-preparation reactor, hydrogen manufacturing conversion furnace and reformation Hydrogen production process.

Background technique

Hydrogen is not only important industrial chemicals and a kind of clean fuel.Hydrogen is in modern industry, especially petroleum It is played an increasingly important role in the national economy such as work industry, fuel cell.In the continuous heaviness of global crude oil, in poor quality Trend is aggravated and people are continuously increased clear gusoline quantity demand, quality standard is constantly promoted, and environmental legislation is constantly stringent Multiple pressure under, it is also increasing to hydrogen demand, and then higher requirements are also raised to device for producing hydrogen.

Process for making hydrogen mainly has water electrolysis method, light hydrocarbon steam conversion method, partial oxidation process and methanol decomposition method etc., at present With being most widely light hydrocarbon steam conversion method.The raw material of light hydrocarbon steam conversion method hydrogen manufacturing is with natural gas, naphtha, refinery Based on the carbon containing light hydrocarbons such as gas.Its conversion process are as follows: light hydrocarbons and water vapour are in certain temperature, pressure and catalyst It reacts under effect, generates hydrogen and carbon monoxide, carbon monoxide further generate hydrogen using water gas shift reaction, Further increase light hydrocarbons purpose product yield.

The main chemical reactions occurred in hydrogen-making reaction procedure have:

Conversion reaction C_nH_m+n H₂O→n CO+(n+m/2)H₂△ H=206kJ/mol

Conversion reaction CO+H₂O→CO₂+H₂△ H=-36kJ/mol

Conversion reaction is a strong endothermic reaction, in traditional SECTION TUBE FOR HYDROGEN MANNU-FACTURING FURNACE, by fuel combustion, will be filled with conversion and urges The reformer tube of agent is heated to 900~1000 DEG C of progress hydrogen production reactions.Common reformation hydrogen production active component have Pt, Pd, Ir, Rh DengV Ш race transition elements limits industrial application due to its price height.Reformation hydrogen production industrial application is the most extensive at present Active component be nickel.Catalyst activity height is directly related with catalyst specific surface axial extent, and in contrast, specific surface is got over Greatly, the dispersion degree of active component is better, and activated centre number is more, to improve the catalytic activity of catalyst.

Existing hydrogen manufacturing conversion furnace loads the nickel-base catalyst of certain granules size, shape in boiler tube, often will appear Filling is uneven, causes unstripped gas bias current, causes feed stock conversion low, and the easy carbon distribution inactivation of catalyst reduces the operation week of device Phase.In addition, the lesser catalyst of loaded particles size in boiler tube increases catalyst although the loadings of catalyst can be improved Activated centre number improves the processing capacity and conversion ratio of raw material to a certain extent, is disadvantageous in that catalyst size is got over Small, boiler tube pressure drop is bigger, increases the energy consumption of feed gas compressor.

Summary of the invention

Purpose of this disclosure is to provide a kind of reforming hydrogen-preparation reactor, reformation hydrogen production reburner and reformation hydrogen production reaction sides Method, the pressure drop of the reburner of the reforming hydrogen-preparation reactor and use reforming hydrogen-preparation reactor are low, existing without gas bias current and short circuit As；Using the method high conversion rate of the reformation hydrogen production reburner.

To achieve the goals above, disclosure first aspect provides a kind of reforming hydrogen-preparation reactor, which includes circle Shaped seals pressure-bearing shell, air inlet, gas outlet, the first straight tube for extending into from the case top enclosure interior, from described Housing bottom extend into the second straight tube of enclosure interior and to be arranged in the shell below first straight tube described second straight Catalysis reaction member above pipe；The air inlet is connected to first straight tube, and the gas outlet and second straight tube connect It is logical；The top and bottom of the catalysis reaction member are sealed by top sealing plate and sealed bottom plate respectively, the catalysis reaction Unit includes the central tube being axially arranged, and the central tube passes through top sealing plate and the first straight tube is in fluid communication；The catalysis Annular space is formed between reaction member lateral wall and the inner wall of shell；The side wall point of the central tube and the catalysis reaction member It is not formed with aperture, so that the central tube is connected to by the aperture with the annular fluid；The sealed bottom plate and institute State the air collecting chamber for being formed between the inner wall of lower part of the housing and being connected to the annular fluid, the annular space by the air collecting chamber with The second straight tube connection；Micro- catalysis reaction plate, the plate face load of the catalysis reaction plate are equipped in the catalysis reaction member There is reforming hydrogen-production catalyst.

Optionally, micro- catalysis reaction plate is axially extended and is spirally distributed around the central tube, described micro- The top and the top sealing plate for being catalyzed reaction plate are tightly connected, the bottom end of micro- catalysis reaction plate and the sealed bottom Plate is tightly connected.

Optionally, micro- catalysis reaction plate is multiple annular plates of one or coaxial arrangement, micro- catalysis reaction plate Inward flange be sealedly and fixedly connected with the catalysis reaction member inner sidewall, it is described it is micro- catalysis reaction plate outer edge urged with described Change reaction member lateral wall to be sealedly and fixedly connected.

Optionally, micro- catalysis reaction plate is selected from least one of surface plate, castellated plates, corrugated plating and corrugated sheet.

The second aspect of the disclosure provides a kind of reformation hydrogen production reburner, including air inlet pipe, escape pipe, burner and burning Room, the reburner further include the reforming hydrogen-preparation reactor of disclosure first aspect, and the reforming hydrogen-preparation reactor is located at the combustion Interior is burnt, the air inlet of the reforming hydrogen-preparation reactor is connected to the air inlet pipe, the gas outlet of the reforming hydrogen-preparation reactor It is connected to the escape pipe.

The third aspect of the disclosure provides anti-using the reformation hydrogen production reburner progress reformation hydrogen production of disclosure second aspect The method answered is fired method includes the following steps: (1) makes fuel gas and air spray into the combustion chamber by the burner It burns；(2) unstripped gas and vapor is made to enter the reforming hydrogen-preparation reactor through the air inlet pipe of the reburner, it is anti-in the catalysis It answers and carries out reformation hydrogen production reaction in unit, obtain the conversion gas rich in hydrogen.

Optionally, it is 700~1100 DEG C that the condition of the reformation hydrogen production reaction, which includes: reaction temperature, reaction pressure 1.8 ~5.5MPaG, the H in vapor₂The molar ratio of carbon atom in O and unstripped gas is (2.5~5): 1, air speed is 1000~ 100000h^-1。

Optionally, mean flow rate of the unstripped gas in the catalysis reaction member is 0.001~100m/s.

Optionally, the unstripped gas is natural gas, liquefied petroleum gas, refinery gas, the resolution gas and stone for reforming hydrogen concentrate PSA At least one of cerebrol.

Optionally, the reformation hydrogen production catalysts include reformation hydrogen production active component, the reformation hydrogen production active group Divide includes at least one of nickel, ruthenium, platinum, palladium, iridium and rhodium.

Compared with prior art, the invention has the benefit that

(1) the catalysis reaction member of reforming hydrogen-preparation reactor is the radial reaction zone being made of micro- catalysis reaction plate, reaction Load has the catalyst of hydrogen production reaction on plate, Distance Shortened of the reaction gas from gas phase main diffusion to catalytic active center, greatly It reduces resistance to mass tranfer (diffusional resistance is almost nil) greatly, while the product generated can be diffused into bodies of fluid, product quickly The residence time is shorter in the reactor, fundamentally improves the transformation efficiency of hydrogen production reaction, reaches and improves unit catalyst production The purpose of product space-time yield.

(2) reaction gas is uniformly distributed into radial reaction zone from central tube and flows from inside to outside, and flow area is gradually Increase, it is mobile to product direction to be conducive to the increased hydrogen production reaction of volume.In addition, as reaction stream flows from inside to outside, outside Layer it is micro- catalysis reaction plate temperature be higher than the micro- catalysis reaction plate of internal layer, the temperature highest of micro- catalysis reaction plate at annular space, Since hydrogen production reaction is an endothermic reaction, be conducive to the progress of hydrogen production reaction.

(3) compared with the reforming hydrogen-preparation reactor of loaded particles shape, using micro- catalysis reaction plate, activity used in reactor Total metal content significantly reduces, pressure drop is low.Under the conditions of same treatment scale, the reforming hydrogen-preparation reactor of the disclosure and it is made of it Reburner equipment size it is more traditional small by 5%~30%, pressure drop low 3%~55%.

(4) compared with the reforming hydrogen-preparation reactor of loaded particles shape, micro- catalysis of the reforming hydrogen-preparation reactor of the disclosure is anti- Plate is answered to be not easy carbon distribution inactivation, long service life, pressure drop is low, and bed pressure drop is low compared with the reactor of same treating capacity (15%~90%)；

(5) catalysis reaction member is made of micro- catalysis reaction plate, is increased activated centre quantity, is improved reaction gas and exist The uniformity at catalytic reaction activity center avoids the occurrence of reaction dead zone and gas Biased flow phenomenon, can fully ensure that whole service Even running in period.

(6) different types of reburner can be suitable for as reformation hydrogen production reformer tube, use scope is wide, and can root Control and tune are reached by the integration mode of the sleeve with functionalization and the increase and decrease of quantity according to actual demand of industrial production Section production, is advantageously implemented the maximum utilization efficiency of equipment, without obvious enlarge-effect, while shortening the process time of equipment, into One step reduces reactor production cost.

Other feature and advantage of the disclosure will the following detailed description will be given in the detailed implementation section.

Detailed description of the invention

Attached drawing is and to constitute part of specification for providing further understanding of the disclosure, with following tool Body embodiment is used to explain the disclosure together, but does not constitute the limitation to the disclosure.In the accompanying drawings:

Fig. 1 is a kind of structural schematic diagram of specific embodiment of the reforming hydrogen-preparation reactor of the disclosure；

Fig. 2 is a kind of cross-sectional view (the i.e. face A-A in Fig. 1 of specific embodiment of the reforming hydrogen-preparation reactor of the disclosure Cross-sectional view)；

Fig. 3 is a kind of catalysis reaction member side wall signal of specific embodiment of the reforming hydrogen-preparation reactor of the disclosure Figure；

Fig. 4 is a kind of schematic diagram of the top sealing plate of specific embodiment of the reforming hydrogen-preparation reactor of the disclosure；

Fig. 5 is the structural schematic diagram of second of specific embodiment of the reforming hydrogen-preparation reactor of the disclosure；

Fig. 6 is cross-sectional view (the i.e. face A-A in Fig. 5 of second of specific embodiment of the reforming hydrogen-preparation reactor of the disclosure Cross-sectional view)；

Fig. 7 is a kind of composition reactor catalysis reaction member of specific embodiment of the reforming hydrogen-preparation reactor of the disclosure Triangular prism shaped component structure diagram used in side wall；

Fig. 8 is a kind of composition reactor catalysis reaction member of specific embodiment of the reforming hydrogen-preparation reactor of the disclosure Cylinder shape assembly structural schematic diagram used in side wall；

Fig. 9 is the structural schematic diagram of the third specific embodiment of the reforming hydrogen-preparation reactor of the disclosure；

Figure 10 is cross-sectional view (the i.e. face A-A in Fig. 9 of the third specific embodiment of the reforming hydrogen-preparation reactor of the disclosure Cross-sectional view)；

Figure 11 is the structural schematic diagram of the 4th kind of specific embodiment of the reforming hydrogen-preparation reactor of the disclosure；

Figure 12 is cross-sectional view (the i.e. A-A in Figure 11 of the 4th kind of specific embodiment of the reforming hydrogen-preparation reactor of the disclosure The cross-sectional view in face)；

Figure 13 is a kind of knot of the micro- catalysis reaction plate of the tooth form of specific embodiment of the reforming hydrogen-preparation reactor of the disclosure Structure schematic diagram；

Figure 14 is a kind of knot of the micro- catalysis reaction plate of the ripple of specific embodiment of the reforming hydrogen-preparation reactor of the disclosure Structure schematic diagram；

Figure 15 is a kind of knot of the micro- catalysis reaction plate of the waveform of specific embodiment of the reforming hydrogen-preparation reactor of the disclosure Structure schematic diagram；

Figure 16 is a kind of structural schematic diagram of specific embodiment of the reformation hydrogen production reburner of the disclosure；

Figure 17 is the structural schematic diagram of another specific embodiment of the reformation hydrogen production reburner of the disclosure；

Figure 18 is the structural schematic diagram of the 5th kind of specific embodiment of the reforming hydrogen-preparation reactor of the disclosure；

Figure 19 is cross-sectional view (the i.e. A-A in Figure 18 of the 5th kind of specific embodiment of the reforming hydrogen-preparation reactor of the disclosure The cross-sectional view in face)；

Figure 20 is the cross-sectional view of the 6th kind of specific embodiment of the reforming hydrogen-preparation reactor of the disclosure；

Figure 21 is the cross-sectional view of the 7th kind of specific embodiment of the reforming hydrogen-preparation reactor of the disclosure；

Figure 22 is the structural schematic diagram of the 8th kind of specific embodiment of the reforming hydrogen-preparation reactor of the disclosure；

Figure 23 is the structural schematic diagram of the 9th kind of specific embodiment of the reforming hydrogen-preparation reactor of the disclosure；

Figure 24 is the structural schematic diagram of the tenth kind of specific embodiment of the reforming hydrogen-preparation reactor of the disclosure；

Figure 25 is a kind of the tenth schematic diagram of specific embodiment of the reforming hydrogen-preparation reactor of the disclosure；

Figure 26 is a kind of central tube schematic diagram of specific embodiment of the reforming hydrogen-preparation reactor of the disclosure；

Figure 27 is the central tube schematic diagram of the reforming hydrogen-preparation reactor another kind specific embodiment of the disclosure.

Description of symbols

The gas outlet 1- air inlet 2- 3- upper cover 4- lower head

5- top sealing plate 6- central tube 7- annular space 8- sealed bottom plate

Micro- the first straight tube of catalysis reaction plate 11- of 9- air collecting chamber 10-

12- shell 14- the second straight tube 15- is catalyzed reaction member lateral wall

16- cushion chamber 17- is catalyzed reaction member inner sidewall 20- reformation hydrogen production reburner

The combustion chamber 21- reforming hydrogen-preparation reactor 22- 23- burner

24- air inlet pipe 25- escape pipe.

Specific embodiment

It is described in detail below in conjunction with specific embodiment of the attached drawing to the disclosure.It should be understood that this place is retouched The specific embodiment stated is only used for describing and explaining the disclosure, is not limited to the disclosure.

In the disclosure, in the absence of explanation to the contrary, the noun of locality used such as " upper and lower, top, bottom " is usually Refer to upper and lower, top and bottom of the device under normal operating condition, can specifically refer to the page of Fig. 1." inside and outside " It is for the profile of device itself.In addition, term " first ", " second " are used for description purposes only, and should not be understood as Indication or suggestion relative importance or the quantity for implicitly indicating indicated technical characteristic." first ", " are defined as a result, Two " feature can explicitly or implicitly include one or more of the features.In the description of the disclosure, " multiples' " It is meant that two or more, unless otherwise specifically defined.

The first aspect of the disclosure provides a kind of reforming hydrogen-preparation reactor, which includes cylinder-shaped seal and pressure bearing shell 12, air inlet 1, gas outlet 2, the first straight tube 11 for extending at the top of shell 12 enclosure interior, extend into from 12 bottom of shell Second straight tube 14 of enclosure interior and the catalysis reaction that second straight tube, 14 top below first straight tube 11 is arranged in shell 12 are single Member 13；Air inlet is connected to the first straight tube 11, and gas outlet 2 is connected to the second straight tube 14；It is catalyzed the top and bottom of reaction member 13 Portion is sealed by top sealing plate 5 and sealed bottom plate 8 respectively, and catalysis reaction member 13 includes the central tube 6 being axially arranged, center Pipe 6 passes through top sealing plate 5 and the first straight tube 11 is in fluid communication；It is catalyzed between reaction member lateral wall 15 and the inner wall of shell 12 It is formed with annular space 7；Central tube 6 and catalysis reaction member 13 side wall be respectively formed with aperture so that central tube 6 by aperture with Annular space 7 is in fluid communication；The air collecting chamber being in fluid communication with annular space 7 is formed between the inner wall of 12 lower part of sealed bottom plate 8 and shell 9, annular space 7 is connected to by air collecting chamber 9 with the second straight tube 14；It is catalyzed in reaction member 13 and is equipped with micro- catalysis reaction plate 10, catalysis is anti- Answering the plate face of plate to load has reforming hydrogen-production catalyst.

The reforming hydrogen-preparation reactor of the disclosure uses micro- catalysis reaction plate, work needed for load has hydrogen production reaction on reaction plate Property component, reduce catalytically-active metals dosage and catalyst be not easy carbon distribution inactivation, shorten reaction gas diffuse to catalysis live The distance at property center, reduces resistance to mass tranfer and reactor pressure decrease, improves hydrogen production reaction conversion ratio；Reaction gas is in reactor In flowed outward by center, flow area, which is gradually increased, reacts plate temperature gradually rises, and increases advantageous as volume and absorbs heat The promotion of the hydrogen production reaction conversion ratio of reaction；The reforming hydrogen-preparation reactor use scope is wide, and the boiler tube as hydrogen manufacturing conversion furnace can To be suitable for different types of reburner.

The reforming hydrogen-preparation reactor of disclosure meaning is usually also referred to as HK-40 Tube at Hydrogen Reformer or reburner in the industrial production Pipe, in no special instruction, three of the above address indicates identical device.According to the disclosure, micro- catalysis reaction plate can To have reforming hydrogen-production catalyst in optional plate face load, can also load in two plate faces of micro- catalysis reaction plate has Reforming hydrogen-production catalyst, preferably two equal supported catalysts of plate face carry out turning for hydrogen production reaction to further increase reactor Rate.Reforming hydrogen-production catalyst can use catalytic active component well-known to those skilled in the art, such as the activity of load Component can be the metals such as nickel, ruthenium, platinum, palladium, iridium and rhodium with reformation hydrogen production reactivity；The load, which refers to, to lead to The methods of dipping, ion sputtering, coating or filling is crossed to load to active component by the catalyst containing active component or directly On micro- catalysis reaction plate.Wherein, active metal component coating loading process can use packet well-known to those skilled in the art Include the coating method in two stages of pretreatment and catalyst deposit of metallic matrix.

According to the disclosure, micro- catalysis reaction plate 10 can along reactor axis to or radially extend or micro- catalysis reaction plate 10 extending direction and horizontal direction are in angle theta, and 0 ° < θ < 90 °.It may include that one or more is micro- in catalysis reaction member 13 to urge Change reaction plate 10, multiple micro- catalysis reaction plates 10 can arrange in catalysis reaction member 13 by the usual manner of this field, only Guarantee that reactor feed gas is being catalyzed reaction member 13 from center radial motion around.It is former in order to further enhance reaction The contact for expecting gas with catalyst on micro- catalysis reaction plate 10, in a kind of specific embodiment of the disclosure, such as Figure 18-21 institute Show, the micro- catalysis reaction plate 10 being catalyzed in reaction member 13 can be axially extended and is spirally distributed around central tube 6, micro- The top of catalysis reaction plate 10 can be tightly connected with top sealing plate 5, and the bottom end of micro- catalysis reaction plate 10 can be close with bottom Sealing plate 8 is tightly connected.

In another embodiment specific implementation mode, as shown in Figs. 1-2, in order to further decrease reactor pressure decrease, adapt to hydrogen manufacturing The characteristics of reaction volume increases, micro- catalysis reaction plate 10 are multiple annular plates of one or coaxial arrangement, micro- catalysis reaction plate 10 Inward flange can with catalysis reaction member inner sidewall 17 be sealedly and fixedly connected, it is micro- catalysis reaction plate 10 outer edge can with urge Change reaction member lateral wall 15 to be sealedly and fixedly connected, the angle theta of cricoid micro- catalysis reaction plate 10 and horizontal direction is preferably 0 ° ~45 °, micro- catalysis reaction plate 10 cricoid at this time preferably radially extends, i.e., angle theta is 0 °.

According to the disclosure, reforming hydrogen-preparation reactor uses load to have micro- catalysis reaction plate 10 of reforming hydrogen-production catalyst can be with Total dosage of catalytically-active metals in reactor is reduced, reduces reactor size, reduce reactor pressure decrease, wherein micro- catalysis is reacted Plate 10 can be this field conventional kind.Catalytic active center number in reactor in order to further increase, it is preferable that micro- catalysis Reaction plate 10 can for selected from least one of surface plate, castellated plates, corrugated plating and corrugated sheet, as Figure 19, Figure 20, Figure 21, Shown in Figure 13, Figure 14, Figure 15, more preferably at least one of castellated plates, corrugated plating and corrugated sheet.Wherein castellated plates, ripple The structure snd size of plate and corrugated sheet with no restrictions, as long as meet load active component, meet process for making hydrogen condition requirement. Micro- catalysis reaction plate number is loaded in order to improve in catalysis reaction member, the preferably same micro- catalysis reaction of type in reactor Plate.Further, for the ease of producing, being installed as reaction plate, while it being uniformly distributed unstripped gas, each piece of micro- catalysis reaction plate Tooth waveform size, type, density degree etc. are answered completely the same, and the present invention does not do tooth waveform size, type, density degree Concrete restriction, as long as meeting hydrogen production reaction process conditions.

According to the disclosure, under identical reaction condition and reactor diameter, the quantity of catalysis reaction member 13 can increase The contact probability for adding reaction gas and catalyst improves the effect of conversion ratio.Catalysis can be adjusted according to real reaction situation The quantity of reaction member 13, such as the quantity of catalysis reaction member 13 can be 1~500, preferably 1~300.In order to mention High reaction raw materials distribution consistency degree, it is preferable that catalysis reaction member 13, central tube 6 and shell 12 are arranged in coaxial manner, multiple Catalysis reaction member can be coaxially disposed.In this case, it is catalyzed between reaction member inner sidewall 17 and the tube wall of central tube 6 And could be formed with cushion chamber 16 between the barrel of two adjacent catalysis reaction members 13, in order to which reactor feed gas is slow It rushes and intracavitary further evenly distributes.In a kind of specific embodiment of the disclosure, as shown in figure 9, catalysis reaction member can be with Including the multiple catalysis reaction members 13 being coaxially arranged；In other embodiments, multiple catalysis reaction members 13 are coaxial up and down Arrangement.

According to the disclosure, in order to extend the service life of micro-reaction plate, central tube 6, micro- catalysis reaction plate can be using gold Belong to material, ceramic material, it is preferred to use the metal material not reacted with the gas in reaction system.The longevity is used in order to extend Life, top sealing plate 5, sealed bottom plate 8 can be equipped with expansion joint, as shown in Figure 4.

According to the disclosure, the relative size for being catalyzed reaction member 13 and central tube 6 can change in a big way, this public affairs It opens and does not do particular/special requirement.The tube wall of the side wall and central tube 6 that are catalyzed reaction member 13 can be about the inferior net of writing brush, perforated panel, prism Shape or it is cylindrical constitute at least one of wall surface, Johnson Net is known to those skilled in the art, and the present invention is herein not It repeats again.Preferably, the tube wall of the side wall and central tube 6 that are catalyzed reaction member 13 can be perforated panel, the aperture shape of perforated panel Formula can be circular hole as shown in figure 26 or groove profile as shown in figure 27, and the shape of aperture, aperture size, aperture (are opened Porosity) present invention with no restrictions, as long as meeting reforming hydrogen producing process condition.

According to the disclosure, the material that the shell of reforming hydrogen-preparation reactor, upper lower head use can be with conventional reformation hydrogen manufacturing The material of boiler tube selection is identical, such as: HP-40Nb, reforming hydrogen-preparation reactor shell material are well known to those skilled in the art , the present invention repeats no more.The specific size of reforming hydrogen-preparation reactor can also change in a big way.Further, it is Adapt to newly-built hydrogen manufacturing conversion furnace unit scale or the upgrading of existing hydrogen manufacturing conversion furnace plant modification, the reformation hydrogen production reaction of the disclosure The reactor inside diameter of device can be 30~1000mm, preferably 50~300mm；Reaction member length is catalyzed in reactor to be 1000mm~30000mm, preferably 3000mm~15000mm.

As shown in Figure 1, mobility status of the reactor feed gas in the reforming hydrogen-preparation reactor of the disclosure may include: reaction Unstripped gas from reactor air inlet 1 through the first straight tube 11 enter catalysis reaction member 13 central tube 6, through center tube wall aperture into Enter cushion chamber 16 to collect, under the further buffering of cushion chamber 16, reallocation effect, reaction stream continues flowing outward, uniformly It radially into catalysis reaction member 13, and flows radially outward, reactor feed gas reacts while outside flowing in micro- catalysis The catalyst active center of 10 area load of plate reacts, and reaction stream continues flowing outward, passes through catalysis reaction member 13 Tube wall opening flow to annular space 7 outward and collect, into air collecting chamber 9, reformation hydrogen production is left by the second straight tube 14, gas outlet 2 Reactor.

As shown in figs. 16-17, the second aspect of the disclosure provides a kind of reformation hydrogen production reburner, including air inlet pipe 24, goes out Tracheae 25, burner 23 and combustion chamber 22, the reburner further include the reforming hydrogen-preparation reactor 21 of disclosure first aspect, reform system Hydrogen reactor 21 is located in combustion chamber 22, and the air inlet 1 of reforming hydrogen-preparation reactor 21 is connected to air inlet pipe 24, reformation hydrogen production reaction The gas outlet 2 of device is connected to escape pipe 25.

According to the disclosure, reformation hydrogen production reburner can be this field conventional kind, such as can burn for tipburn furnace, side At least one of furnace, bottom fired heater and trapezoidal furnace, tipburn furnace preferably as shown in figure 16 and/or side as shown in figure 17 are burnt Furnace.Burner, fuel type etc. are not done specifically limited in reburner, as long as can satisfy energy needed for reformation hydrogen production.In addition, The disclosure is not particularly limited the reactor quantity being mounted between reburner air inlet pipe, escape pipe and arrangement mode etc., As long as meeting the requirement of reforming hydrogen producing process condition.

The reformation hydrogen production converting furnace pressure drop of the disclosure is low, in boiler tube per volume of catalyst product space-time yield Height, and reburner overall dimensions are small, reduce equipment investment and energy consumption.

The third aspect of the disclosure provides anti-using the reformation hydrogen production reburner progress reformation hydrogen production of disclosure second aspect The method answered is burnt method includes the following steps: (1) makes fuel gas and air spray into combustion chamber by burner；(2) make The air inlet pipe of unstripped gas and the inverted furnace of vapor enters reforming hydrogen-preparation reactor, carries out reformation system in catalysis reaction member 13 Hydrogen reaction, obtains the conversion gas rich in hydrogen.

The reformation hydrogen production reaction method reformer tube internal pressure reduction of the disclosure, unstripped gas high conversion rate, can satisfy hydrogen manufacturing Reaction requires.

In the reformation hydrogen production reaction method according to the disclosure, the condition of reformation hydrogen production reaction can become in a big way Change, it is preferable that the reaction temperature in reforming hydrogen-preparation reactor can be 700~1100 DEG C, preferably 800~950 DEG C；Reaction pressure Power can be 1.8~5.5MPaG, preferably 1.8~3.5MPaG, the H in vapor₂Mole of O and the carbon atom in unstripped gas Than that can be (2.5~5): 1, preferably (2.5~4): 1.Under above-mentioned preferred reaction condition, the reformation hydrogen production of the disclosure reacts Conversion ratio is higher.

Further, in order to improve unstripped gas conversion ratio, unstripped gas air speed can be 1000~100000h^-1, further excellent Select 3000~90000h^-1, most preferably 8000~70000h^-1。

In order to improve unstripped gas conversion ratio, mean flow rate of the unstripped gas in catalysis reaction member can be 0.3~90m/ s.Further, it axially extends and surrounds in the embodiment that central tube 6 is spirally distributed, raw material in micro- catalysis reaction plate Gas can be 0.003~90m/s, preferably 0.1~75m/s by the mean flow rate of the helicoidal structure of micro- catalysis reaction plate； In the embodiments of multiple cricoid micro- catalysis axially spaced settings of reaction plate 10, mean flow rate that unstripped gas passes through can be with For 0.001~100m/s, preferably 0.3~90m/s.

In the reformation hydrogen production reaction method according to the disclosure, reactor feed gas can be natural gas, liquefied petroleum gas, refining At least one of factory's gas, the resolution gas for reforming hydrogen concentrate PSA and naphtha.Wherein, natural gas mainly becomes methane, and contains The small molecules such as a small amount of ethane hydro carbons, carbon dioxide and nitrogen etc., the sulfur content in natural gas is low, and predominantly hydrogen sulfide, sulphur Alcohol, hydroxyl sulphur etc. are easy to be removed by simple hydrotreating；Refinery gas is primarily referred to as crude(oil)unit Fixed gas, catalysis drying gas, coking dry gas plus hydrogen dry gas and reformation dry gas etc.；Liquefied petroleum gas main component be propane, propylene, Butane, butylene, can be the mixture of one or more of above-mentioned hydrocarbon, and contain a small amount of pentane, amylene and trace sulfide impurity, Wherein carbonyl sulfide is removed with hydramine absorption tower, and removes sulphide removal with alkali wash；It reforms and contains in the resolution gas of hydrogen concentrate PSA About a large amount of hydrogen and some small molecule hydro carbons；The preferentially sequence of naphtha are as follows: doing 70 DEG C of perfectly straight light naphthar, (reformation is pulled out Hair oil), refinery's narrow fraction reforming raffinate oil, the perfectly straight gasoline of full fraction for doing 146 DEG C, one way hydrocracked naphtha.

In the reformation hydrogen production reaction method according to the disclosure, steam refers to middle pressure steam, and temperature can be 420 DEG C of left sides Right, pressure can be 3.5Mpa or so, and the temperature, pressure of steam are it is possible that fluctuation, the disclosure during practical distribution It is not particularly limited, as long as meeting process for making hydrogen needs condition.

In the reformation hydrogen production reaction method according to the disclosure, reformation hydrogen production catalysts can be conventional kind of this field Class, for example, reformation hydrogen production catalysts may include reformation hydrogen production active component, reformation hydrogen production active component may include At least one of nickel, ruthenium, platinum, palladium, iridium and rhodium.

The present invention is further illustrated by embodiment below in conjunction with attached drawing, but therefore the disclosure is not taken office What is limited.

Embodiment 1

As shown in Figure 1, Figure 2, shown in Fig. 3, Fig. 4, Figure 15, reforming hydrogen-preparation reactor used by the present embodiment includes containing upper end It is equipped with the pressure-bearing shell 12 of the second straight tube 14 equipped with the first straight tube 11, lower end, is equipped with cylindrical catalytic reaction member 13 in shell, urges Changing reaction member 13 includes the central tube 6 that is axially arranged, and the top of the first straight tube 11 is provided with air inlet 1, under the second straight tube 14 Portion is provided with gas outlet 2.The waveform catalysis reaction plate that catalysis reaction member is arranged by horizontal parallel is constituted, and central tube 6, tubular are urged Change reaction member 13 and shell 12 to arrange in coaxial manner；It is catalyzed micro- catalysis reaction plate 10 of reaction member 13 and catalysis reacts single First lateral wall 15, catalysis reaction member inner sidewall 17 are connected and fixed；It is catalyzed reaction member lateral wall 15, catalysis reaction member inside Wall 17 is connected and fixed with top sealing plate 5, sealed bottom plate 8 respectively；Central tube 6 uses circular opening, and percent opening 16.8% is micro- Catalytic active component NiO needed for catalysis 10 liang of lateral loads of reaction plate have reformation hydrogen production to react.

The internal diameter of reforming hydrogen-preparation reactor is 130mm, tangential length 11500mm, inner diameter of centerpipe 25mm, radial catalysis Reaction member height 9500mm, the adjacent two micro- catalysis reaction plate for being catalyzed reaction member 13 divide in catalysis 13 diameter two of reaction member One of place's spacing be 1mm, annular space distance be 5mm, be catalyzed the adjacent micro-reaction plate of reaction member 13 between mean flow rate be 0.02m/s。

Reactor shell material uses HP40-Nb (containing the elements such as Cr, Ni, Nb, W, Mo, Ti), micro- catalysis reaction plate 10 Using Fe-Cr-Al/Al₂O₃Material material is catalysis load substrate, and is waveform substrate, and peaks and troughs distance is 2.5mm, together The distance between two adjacent peaks or adjacent trough are 5mm on one micro- catalysis reaction plate, and substrate two sides supported active metals are NiO, content 17.5%.

The reformation hydrogen production reburner of the present embodiment is as shown in figure 16, including above-mentioned reforming hydrogen-preparation reactor 21, air inlet pipe 24, Escape pipe 25, burner 23 and combustion chamber 22, reforming hydrogen-preparation reactor 21 are located in combustion chamber 22, reforming hydrogen-preparation reactor 21 into Port 1 is connected to air inlet pipe 24, and the gas outlet 2 of reforming hydrogen-preparation reactor is connected to escape pipe 25.

The reforming hydrogen-preparation reactor of the present embodiment and reburner are reacted applied to natural gas steam reformation hydrogen production, it is main to walk Suddenly include:

1) so that the burner 23 of fuel gas and the inverted furnace of air is sprayed into combustion chamber 22, make fuel in the combustion chamber of reburner Burning provides hydrogen production reaction institute calorific requirement, and temperature of reactor is 910 DEG C；

2) make water vapour and CH₄The mixed gas (500 DEG C of temperature, pressure 3.0MPaG) that molar ratio is 3.1, flow is 30kmol/h, air speed 42300h^-1, reburner air inlet pipe is entered after being sufficiently mixed, by the first straight tube of reactor 11, then successively Into central tube 6, cushion chamber 16, sleeve 15 micro- catalysis reaction plate on carry out reformation hydrogen production reaction, conversion after reacting Gas leaves reactor by annular space 7, air collecting chamber 9, the second straight tube 14, into conversion furnace outlet duct 25, will be enriched in the conversion of hydrogen Gas is expelled to outside reburner.It is detected, outlet methane content (not moisture vapor) is 0.2%.

Provided in table 1 be the reforming hydrogen-preparation reactor and same reactor size in the prior art of the present embodiment and it is identical It is catalyzed the hydrogen-manufacturing reactor comparative situation of reaction member size.From reactor bed pressure drop, CH₄Three conversion ratio, air speed indexs As can be seen that the reactor of the present embodiment all shows excellent performance, reactor pressure decrease especially is being reduced, is improving reaction Advantage in terms of device air speed is especially prominent.

The reforming reactor and conventional hydrogen production reactor of 1 the present embodiment of table compare

Type of reactor	Pressure drop, MPa	CH₄Conversion ratio/(%)	Air speed, h^-1
				Conventional reactor	0.33	95	3400
The reactor of the present embodiment	0.06	≥99	42300

Embodiment 2

As shown in Fig. 2, Fig. 3, Fig. 4, Fig. 5, the reforming hydrogen-preparation reactor and reburner of the present embodiment and reacting for embodiment 1 Device size, adjacent two catalysis reaction plate spacing, annular space distance, the basic material of micro-reaction plate and unit area active component NiO Load capacity parameter is identical.Difference from Example 1 is that micro- catalysis reaction plate is plane micro-reaction plate in the present embodiment.Together Reason reacts the reactor of the present embodiment and reburner applied to natural gas steam reformation hydrogen production.Process for making hydrogen condition and embodiment 1 is identical, is detected, and outlet methane content (not moisture vapor) is 1.3%.

Provided in table 2 be the reforming hydrogen-preparation reactor and same reactor size in the prior art of the present embodiment and it is identical It is catalyzed the hydrogen-manufacturing reactor comparative situation of reaction member size.From reactor bed pressure drop, CH₄Three conversion ratio, air speed indexs As can be seen that the reactor of the present embodiment all shows excellent performance, reactor pressure decrease especially is being reduced, is improving reaction Advantage in terms of device air speed is especially prominent.

The reforming reactor and conventional hydrogen production reactor of 2 the present embodiment of table compare

Type of reactor	Pressure drop, MPa	CH₄Conversion ratio/(%)	Air speed, h^-1
				Conventional reactor	0.33	95	3400
The reactor of the present embodiment	0.05	≥97	42300

Embodiment 3

As shown in Fig. 5, Fig. 6, Fig. 7, the reforming hydrogen-preparation reactor and reburner of the present embodiment and the reactor ruler of embodiment 2 Very little, adjacent two catalysis reaction plate spacing, annular space distance, the basic material of micro-reaction plate and unit area active component NiO load It is identical to measure parameter.Difference from Example 2 is, reaction member inner sidewall 17 and catalysis reaction member are catalyzed in the present embodiment Lateral wall 15 is made of regular triangular prism shaped HP40-Nb material, triangular prism side length 9.5mm, the gap spacing that adjacent triangular prism is constituted For 1.5mm.

Similarly the reactor of the present embodiment and reburner are reacted applied to natural gas steam reformation hydrogen production.Process for making hydrogen item Part is same as Example 1, is detected, and outlet methane content (not moisture vapor) is 1.5%.

Provided in table 3 be the reforming hydrogen-preparation reactor and same reactor size in the prior art of the present embodiment and it is identical It is catalyzed the hydrogen-manufacturing reactor comparative situation of reaction member size.From reactor bed pressure drop, CH₄Three conversion ratio, air speed indexs As can be seen that the reactor of the present embodiment all shows excellent performance, reactor pressure decrease especially is being reduced, is improving reaction Advantage in terms of device air speed is especially prominent.

The reforming reactor and conventional hydrogen production reactor of 3 the present embodiment of table compare

Type of reactor	Pressure drop, MPa	CH₄Conversion ratio/(%)	Air speed, h^-1
				Conventional reactor	0.33	95	3400
The reactor of the present embodiment	0.04	≥97.5	42300

Embodiment 4

As shown in Figure 9, Figure 10, the reforming hydrogen-preparation reactor of the present embodiment and reburner, process for making hydrogen condition etc. and implementation The number of example 2 is identical.Difference from Example 2 is, the radial catalysis reaction member that the present embodiment is constituted using two sleeves, two The radial dimension of a sleeve is identical, and the other parameters of sleeve are same as Example 2.

Process for making hydrogen condition is same as Example 1, is detected, and outlet methane content (not moisture vapor) is 1.0%.

Provided in table 4 be the reforming hydrogen-preparation reactor and same reactor size in the prior art of the present embodiment and it is identical It is catalyzed the hydrogen-manufacturing reactor comparative situation of reaction member size.From reactor bed pressure drop, CH₄Three conversion ratio, air speed indexs As can be seen that the reactor of the present embodiment all shows excellent performance, reactor pressure decrease especially is being reduced, is improving reaction Advantage in terms of device air speed is especially prominent.

The reforming reactor and conventional hydrogen production reactor of 4 the present embodiment of table compare

Type of reactor	Pressure drop, MPa	CH₄Conversion ratio/(%)	Air speed, h^-1
				Conventional reactor	0.33	95	3400
The reactor of the present embodiment	0.07	≥98	42300

Embodiment 5

If Figure 11, Figure 12 show, the reforming hydrogen-preparation reactor and reburner of the present embodiment, process for making hydrogen condition etc. and embodiment 1 number is identical.Difference from Example 1 is, on the inside of micro- catalysis reaction plate of the present embodiment sleeve 13 directly and outside central tube 6 Wall is connected and fixed, and eliminates cushion chamber 16, catalysis reaction member inner sidewall 17.

Similarly the reforming hydrogen-preparation reactor of the present embodiment and reburner are reacted applied to natural gas steam reformation hydrogen production.System For hydrogen process conditions in addition to air speed is different from embodiment 1, remaining process conditions is all the same, and the air speed of the present embodiment is 48600.Through examining It surveys, outlet methane content (not moisture vapor) is 1.2%.

Provided in table 5 be the reforming hydrogen-preparation reactor and same reactor size in the prior art of the present embodiment and it is identical It is catalyzed the hydrogen-manufacturing reactor comparative situation of reaction member size.From reactor bed pressure drop, CH₄Three conversion ratio, air speed indexs As can be seen that the reactor of the present embodiment all shows excellent performance, reactor pressure decrease especially is being reduced, is improving reaction Advantage in terms of device air speed is especially prominent.

The reforming reactor and conventional hydrogen production reactor of 5 the present embodiment of table compare

Type of reactor	Pressure drop, MPa	CH₄Conversion ratio/(%)	Air speed, h^-1
				Conventional reactor	0.33	95	3400
The reactor of the present embodiment	0.1	≥98	48600

Embodiment 6

As shown in Figure 11, Figure 12, the reforming hydrogen-preparation reactor and reburner of the present embodiment are same as Example 5.With implementation Example 5 the difference is that, the present embodiment using reform hydrogen concentrate PSA resolution gas as reaction raw materials, resolution gas group is shown in Table 6.Combustion Material burning in the combustion chamber of reburner provides hydrogen production reaction institute calorific requirement, and temperature of reactor is 905 DEG C.Water vapour and CH₄It rubs You are than the mixed gas (500 DEG C of temperature, pressure 3.05MPaG) for 2.5, flow 35kmol/h, air speed 49300h^-1, sufficiently mixed Enter reburner air inlet pipe after conjunction, carries out reformation hydrogen production reaction, hair by the first straight tube of reactor 11, into catalysis reaction member Conversion gas after raw reaction leaves reactor by annular space 7, air collecting chamber 9, the second straight tube 14, will be rich into conversion furnace outlet duct The conversion gas of hydrogen is expelled to outside reburner.It is detected, outlet methane content (not moisture vapor) is 0.75%.

Using the reactor provided in embodiment 5, reaction raw materials, process conditions are different from embodiment, obtained reaction knot Fruit and conventional reactor are shown in Table 7 in the reaction result comparative situation that same reaction raw material and process conditions obtain.From reactor beds Lamination drop, CH₄The reactor that three conversion ratio, air speed indexs can be seen that the present embodiment all shows excellent performance, especially It is to reduce reactor pressure decrease, and the advantage in terms of raising reactor air speed is especially prominent.

Table 6 reforms hydrogen concentrate PSA resolution gas composition

The hydrogen production process reactor and conventional hydrogen production reactor of 7 the present embodiment of table compare

Type of reactor	Pressure drop, MPa	CH₄Conversion ratio/(%)	Air speed, h^-1
				Conventional reactor	0.38	97	4400
The reactor of the present embodiment	0.13	≥99	49300

Embodiment 7

As shown in Figure 18, Figure 19, reforming hydrogen-preparation reactor used by the present embodiment include upper end be equipped with the first straight tube 11, Lower end is equipped with the pressure-bearing shell 12 of the second straight tube 14, and a catalysis reaction member 13 containing central tube 6 is equipped in shell, described The top of first straight tube 11 is provided with air inlet 1, and 14 lower part of the second straight tube is provided with gas outlet 2.Reaction member 13 is catalyzed by micro- Catalysis reaction plate 10 twist arranges that composition, central tube 6 and shell 12 are arranged in coaxial manner around central tube 6；Micro- catalysis is anti- 10 top edge of plate and the catalysis sealing of reaction member top sealing plate 5 is answered to fix, micro- 10 lower edge of catalysis reaction plate is reacted with catalysis The sealing of unit bottom sealing plate 8 is fixed；Catalytic active component needed for micro- 10 liang of lateral loads of catalysis reaction plate have reformation hydrogen production to react NiO。

The internal diameter of reforming hydrogen-preparation reactor is 110mm, tangential length 12500mm, inner diameter of centerpipe 30mm, and micro- catalysis is anti- The length for answering plate 10 is 10000mm, and central tube uses circular opening, and pore size isUniform pore openings, percent opening are 17.5%, adjacent two catalysis reaction plate spacing is 1mm, and the micro- reaction plate and the annular space distance of inner walls of being catalyzed of outermost layer is 3mm, Mean flow rate between micro-reaction plate is 1.3m/s.

Reactor shell material uses HP40-Nb (containing the elements such as Cr, Ni, Nb, W, Mo, Ti), micro- catalysis reaction plate 10 Using Fe-Cr-Al/Al₂O₃Material material is catalysis load substrate, and is planar substrates, and substrate two sides supported active metals are NiO, content 13.5%.

The reforming hydrogen-preparation reactor of the present embodiment and reburner are reacted applied to natural gas steam reformation hydrogen production, it is main to walk Suddenly include: that the burner 23 of fuel gas and the inverted furnace of air 1) is made to spray into combustion chamber 22, make fuel in the combustion chamber of reburner Burning provides hydrogen production reaction institute calorific requirement, and temperature of reactor is 950 DEG C；2) make water vapour and CH₄The gaseous mixture that molar ratio is 3.2 Body (500 DEG C of temperature, pressure 3.2MPaG), flow 44.91kmol/h, air speed 63230h^-1, reburner is entered after being sufficiently mixed Air inlet pipe is entered by the first straight tube of reactor 11, central tube 6 and carries out reformation hydrogen production reaction on micro- catalysis reaction plate, is occurred anti- Conversion gas after answering leaves reactor by catalysis reaction member gas outlet 15, annular space 7, air collecting chamber 9, the second straight tube 14, enters Furnace outlet duct is converted, the conversion gas that will be enriched in hydrogen is expelled to outside reburner.It is detected, exports methane content (not aqueous steaming Vapour) it is 1.45%.

Provided in table 8 be the reforming hydrogen-preparation reactor and same reactor size in the prior art of the present embodiment and it is identical It is catalyzed the hydrogen-manufacturing reactor comparative situation of reaction member size.From reactor bed pressure drop, CH₄Three conversion ratio, air speed indexs As can be seen that the reactor of the present embodiment all shows excellent performance, reactor pressure decrease especially is being reduced, is improving reaction Advantage in terms of device air speed is especially prominent.

A kind of reforming reactor and conventional hydrogen production reactor of 8 the present embodiment of table compare

Type of reactor	Pressure drop, MPa	CH₄Conversion ratio/(%)	Air speed, h^-1
				Conventional reactor	0.33	95	3400
The reactor of the present embodiment	0.05	≥95.5	63230

Embodiment 8

As shown in Figure 18, Figure 20, Figure 13, the reforming hydrogen-preparation reactor and reburner of the present embodiment and reacting for embodiment 7 Device size, adjacent two are catalyzed the annular space distance, micro-reaction plate for reacting the micro- catalysis reaction plate of plate spacing, outermost layer and inner walls Basic material is identical with unit area active component NiO load capacity parameter.Difference from Example 7 is, in the present embodiment Micro- catalysis reaction plate is tooth form micro-reaction plate, and tooth form direction can be for along reactor radial direction.For castellated plates, wave Peak and trough distance are 4mm, and the distance between same micro- two adjacent peaks of shape plate or adjacent trough are 6.5mm.

Similarly the reforming hydrogen-preparation reactor of the present embodiment and reburner are reacted applied to natural gas steam reformation hydrogen production.System Hydrogen process conditions are same as Example 7, detected, and outlet methane content (not moisture vapor) is 1.2%.

Provided in table 9 be the reforming hydrogen-preparation reactor and same reactor size in the prior art of the present embodiment and it is identical It is catalyzed the hydrogen-manufacturing reactor comparative situation of reaction member size.From reactor bed pressure drop, CH₄Three conversion ratio, air speed indexs As can be seen that the reactor of the present embodiment all shows excellent performance, reactor pressure decrease especially is being reduced, is improving reaction Advantage in terms of device air speed is especially prominent.

Another reforming reactor and conventional hydrogen production reactor of 9 the present embodiment of table compare

Type of reactor	Pressure drop, MPa	CH₄Conversion ratio/(%)	Air speed, h^-1
				Conventional reactor	0.33	95	3400
The reactor of the present embodiment	0.062	≥96	63230

Embodiment 9

As shown in Figure 18, Figure 21, Figure 15, the reforming hydrogen-preparation reactor and reburner of the present embodiment and reacting for embodiment 8 Device size, adjacent two are catalyzed the annular space distance, micro-reaction plate for reacting the micro- catalysis reaction plate of plate spacing, outermost layer and inner walls Basic material is identical with unit area active component NiO load capacity parameter.Difference from Example 8 is, in the present embodiment Micro- catalysis reaction plate is waveform micro-reaction plate, and waveform direction is along reactor radial direction.For corrugated sheet, wave crest with Trough distance is 4mm, and the distance between same micro- two adjacent peaks of shape plate or adjacent trough are 6.5mm.

Similarly the reactor of the present embodiment is reacted applied to natural gas steam reformation hydrogen production.Process for making hydrogen condition and implementation Example 7 is identical, is detected, and outlet methane content (not moisture vapor) is 1.30%.

What is provided in table 10 is the reforming hydrogen-preparation reactor and same reactor size and phase in the prior art of the present embodiment With the hydrogen-manufacturing reactor comparative situation of catalysis reaction member size.From reactor bed pressure drop, CH₄Conversion ratio, air speed three fingers Mark is as can be seen that the reactor of the present embodiment all shows excellent performance, and especially in reduction reactor pressure decrease, raising is anti- Answer the advantage in terms of device air speed especially prominent.

The reforming reactor and conventional hydrogen production reactor of 10 the present embodiment of table compare

Type of reactor	Pressure drop, MPa	CH₄Conversion ratio/(%)	Air speed, h^-1
				Conventional reactor	0.33	95	3400
The reactor of the present embodiment	0.06	≥96	63230

Embodiment 10

As shown in Figure 19, Figure 22, the reforming hydrogen-preparation reactor and reburner of the present embodiment, process for making hydrogen condition etc. and implementation 9 parameter of example is identical.Difference from Example 9 is that micro- catalysis reaction plate waveform direction is along reactor axis in the present embodiment It to direction, and is corrugated sheet.

Similarly the reforming hydrogen-preparation reactor of the present embodiment and reburner are reacted applied to natural gas steam reformation hydrogen production.System Hydrogen process conditions are same as Example 7, detected, and outlet methane content (not moisture vapor) is 0.05%.

What is provided in table 11 is the reforming hydrogen-preparation reactor and same reactor size and phase in the prior art of the present embodiment With the hydrogen-manufacturing reactor comparative situation of catalysis reaction member size.From reactor bed pressure drop, CH₄Conversion ratio, air speed three fingers Mark is as can be seen that the reactor of the present embodiment all shows excellent performance, and especially in reduction reactor pressure decrease, raising is anti- Answer the advantage in terms of device air speed especially prominent.

The reforming reactor and conventional hydrogen production reactor of 11 the present embodiment of table compare

Type of reactor	Pressure drop, MPa	CH₄Conversion ratio/(%)	Air speed, h^-1
				Conventional reactor	0.33	95	3400
The reactor of the present embodiment	0.05	≥99	63230

Embodiment 11

It is the reforming hydrogen-preparation reactor and reburner of the present embodiment, process for making hydrogen condition, micro- as shown in Figure 19, Figure 23, Figure 14 It is identical as 10 parameter of embodiment to be catalyzed reaction plate waveform direction and structural parameters etc..Difference from Example 10 is, this reality Applying micro-reaction plate in example is corrugated plating.

Similarly the reforming hydrogen-preparation reactor of the present embodiment and reburner are reacted applied to natural gas steam reformation hydrogen production.System Hydrogen process conditions are same as in Example 10, detected, and outlet methane content (not moisture vapor) is 0.05%.

What is provided in table 12 is the reforming hydrogen-preparation reactor and same reactor size and phase in the prior art of the present embodiment With the hydrogen-manufacturing reactor comparative situation of catalysis reaction member size.From reactor bed pressure drop, CH₄Conversion ratio, air speed three fingers Mark is as can be seen that the reactor of the present embodiment all shows excellent performance, and especially in reduction reactor pressure decrease, raising is anti- Answer the advantage in terms of device air speed especially prominent.

The reforming reactor and conventional hydrogen production reactor of 12 the present embodiment of table compare

Type of reactor	Pressure drop, MPa	CH₄Conversion ratio/(%)	Air speed, h^-1
				Conventional reactor	0.33	95	3400
The reactor of the present embodiment	0.05	≥99.3	63230

Embodiment 12

It is the reforming hydrogen-preparation reactor and reburner of the present embodiment, process for making hydrogen condition, micro- as shown in Figure 19, Figure 24, Figure 13 It is identical as 10 parameter of embodiment to be catalyzed reaction plate waveform direction and structural parameters etc..Difference from Example 10 is, this reality Applying micro-reaction plate in example is castellated plates.

Similarly the reforming hydrogen-preparation reactor of the present embodiment and reburner are reacted applied to natural gas steam reformation hydrogen production.System Hydrogen process conditions are same as in Example 10, detected, and outlet methane content (not moisture vapor) is 0.08%.

What is provided in table 13 is the reforming hydrogen-preparation reactor and same reactor size and phase in the prior art of the present embodiment With the hydrogen-manufacturing reactor comparative situation of catalysis reaction member size.From reactor bed pressure drop, CH₄Conversion ratio, air speed three fingers Mark is as can be seen that the reactor of the present embodiment all shows excellent performance, and especially in reduction reactor pressure decrease, raising is anti- Answer the advantage in terms of device air speed especially prominent.

The reforming reactor and conventional hydrogen production reactor of 13 the present embodiment of table compare

Type of reactor	Pressure drop, MPa	CH₄Conversion ratio/(%)	Air speed, h^-1
				Conventional reactor	0.33	95	3400
The reactor of the present embodiment	0.055	≥99	63230

Embodiment 13

As shown in Figure 19, Figure 25, reforming hydrogen-preparation reactor, process for making hydrogen condition of the present embodiment etc. and 7 parameter of embodiment It is identical.Difference from Example 7 is that the identical micro- catalysis of five structure sizes comprising coaxial arrangement in the present embodiment is anti- Unit is answered, the high 2000mm of reaction member is catalyzed.In addition to topmost, lowest part catalysis reaction member, adjacent catalyst reaction member Top sealing plate 5 and the sealing of sealed bottom plate 8 are fixed, and central tube 6 is connected and fixed and is connected to.

The reformation hydrogen production reburner of the present embodiment is as shown in figure 17, be sidefired furnace, including above-mentioned reforming hydrogen-preparation reactor 21, Air inlet pipe 24, escape pipe 25, burner 23 and combustion chamber 22, reforming hydrogen-preparation reactor 21 are located in combustion chamber 22, and reformation hydrogen production is anti- The air inlet 1 of device 21 is answered to be connected to air inlet pipe 24, the gas outlet 2 of reforming hydrogen-preparation reactor is connected to escape pipe 25.

The present embodiment reforming hydrogen-preparation reactor and reburner are reacted applied to natural gas steam reformation hydrogen production.Process for making hydrogen Condition is same as Example 7.It is detected, outlet methane content (not moisture vapor) is 1.2%.

What is provided in table 14 is the reforming hydrogen-preparation reactor and same reactor size and phase in the prior art of the present embodiment With the hydrogen-manufacturing reactor comparative situation of catalysis reaction member size.From reactor bed pressure drop, CH₄Conversion ratio, air speed three fingers Mark is as can be seen that the reactor of the present embodiment all shows excellent performance, and especially in reduction reactor pressure decrease, raising is anti- Answer the advantage in terms of device air speed especially prominent.

The reforming reactor and conventional hydrogen production reactor of 14 the present embodiment of table compare

Type of reactor	Pressure drop, MPa	CH₄Conversion ratio/(%)	Air speed, h^-1
				Conventional reactor	0.33	95	3400
The reactor of the present embodiment	0.075	≥97.5	63230

Embodiment 14

As shown in Figure 18, Figure 19, the reforming hydrogen-preparation reactor and reburner of the present embodiment are identical as 7 parameter of embodiment.With Embodiment 7 the difference is that, the present embodiment using reform hydrogen concentrate PSA resolution gas as reaction raw materials, resolution gas group is shown in Table 15 fuel burn in the combustion chamber of reburner provides hydrogen production reaction institute calorific requirement, and temperature of reactor is 930 DEG C.Water vapour with CH₄The mixed gas (500 DEG C of temperature, pressure 3MPaG) that molar ratio is 2.8, flow 48.52kmol/h, air speed 68310h^-1, Enter reburner air inlet pipe after being sufficiently mixed, is entered on micro- catalysis reaction plate by the first straight tube of reactor 11, central tube 6 and carried out Reformation hydrogen production reaction, conversion gas after reacting leave reactor by annular space 7, air collecting chamber 9, the second straight tube 14, into turning Change furnace outlet duct, the conversion gas that will be enriched in hydrogen is expelled to outside reburner.It is detected, is exported methane content (not moisture vapor) It is 0.08%.

Using the reactor provided in embodiment 7, reaction raw materials, process conditions are different from embodiment, obtained reaction knot Fruit and conventional reactor are shown in Table 16 in the reaction result comparative situation that same reaction raw material and process conditions obtain.From reactor beds Lamination drop, CH₄The reactor that three conversion ratio, air speed indexs can be seen that the present embodiment all shows excellent performance, especially It is to reduce reactor pressure decrease, and the advantage in terms of raising reactor air speed is especially prominent.

Table 15 reforms hydrogen concentrate PSA resolution gas composition

The reforming reactor and conventional hydrogen production reactor of 16 the present embodiment of table compare

Type of reactor	Pressure drop, MPa	CH₄Conversion ratio/(%)	Air speed, h^-1
				Conventional reactor	0.38	97	4400
The reactor of the present embodiment	0.1	≥99	68310

The reforming hydrogen-preparation reactor and reburner that the disclosure provides are compact-sized, active metal dosage is few；Using the reaction When device carries out reformation hydrogen production reaction, bed pressure drop is small, per volume of catalyst production intensity is big, reactant diffusion path is shorter, Feed stock conversion is high, and no gas bias current and short circuit phenomenon can satisfy the production process of existing steam reforming hydrogen manufacturing.

It can be seen that from the data of embodiment 1-14 from reactor bed pressure drop, CH₄Three conversion ratio, air speed indexs can To find out, the reforming hydrogen-preparation reactor and reburner of the disclosure show excellent performance, are especially reducing reactor pressure It drops, the advantage in terms of raising reactor air speed is especially prominent.

The preferred embodiment of the disclosure is described in detail in conjunction with attached drawing above, still, the disclosure is not limited to above-mentioned reality The detail in mode is applied, in the range of the technology design of the disclosure, a variety of letters can be carried out to the technical solution of the disclosure Monotropic type, these simple variants belong to the protection scope of the disclosure.

It is further to note that specific technical features described in the above specific embodiments, in not lance In the case where shield, it can be combined in any appropriate way.In order to avoid unnecessary repetition, the disclosure to it is various can No further explanation will be given for the combination of energy.

In addition, any combination can also be carried out between a variety of different embodiments of the disclosure, as long as it is without prejudice to originally Disclosed thought equally should be considered as disclosure disclosure of that.

Claims

1. a kind of reforming hydrogen-preparation reactor, which is characterized in that the reactor includes cylinder-shaped seal and pressure bearing shell (12), air inlet (1), gas outlet (2), enclosure interior is extend at the top of the shell (12) the first straight tube (11), from the shell (12) bottom Portion extend into the second straight tube (14) of enclosure interior and is arranged in the shell (12) described in the first straight tube (11) lower section Catalysis reaction member (13) above second straight tube (14)；The air inlet is connected to first straight tube (11), the outlet Mouth (2) is connected to second straight tube (14)；

The top and bottom of catalysis reaction member (13) are sealed by top sealing plate (5) and sealed bottom plate (8) respectively, institute Stating catalysis reaction member (13) includes the central tube (6) being axially arranged, and the central tube (6) passes through top sealing plate (5) and the One straight tube (11) is in fluid communication；Annular space is formed between catalysis reaction member lateral wall (15) and the inner wall of shell (12) (7)；The side wall of the central tube (6) and catalysis reaction member (13) is respectively formed with aperture, so that the central tube (6) It is in fluid communication by the aperture and the annular space (7)；The inner wall of the sealed bottom plate (8) and the shell (12) lower part it Between be formed with the air collecting chamber (9) being in fluid communication with the annular space (7), the annular space (7) passes through the air collecting chamber (9) and described the Two straight tubes (14) connection；Micro- catalysis reaction plate (10), the catalysis reaction plate (10) are equipped in the catalysis reaction member (13) Plate face load have reforming hydrogen-production catalyst.

2. reforming hydrogen-preparation reactor according to claim 1, which is characterized in that micro- catalysis reaction plate (10) is along axial direction Extend and be spirally distributed around the central tube (6), the top and the top of micro- catalysis reaction plate (10) seal Plate (5) is tightly connected, and the bottom end of micro- catalysis reaction plate (10) and the sealed bottom plate (8) are tightly connected.

3. reforming hydrogen-preparation reactor according to claim 1, which is characterized in that micro- catalysis reaction plate (10) is one Or multiple annular plates of coaxial arrangement, the inward flange and the catalysis reaction member inner sidewall of micro- catalysis reaction plate (10) (17) it is sealedly and fixedly connected, the outer edge of micro- catalysis reaction plate (10) and the catalysis reaction member lateral wall (15) seal It is fixedly connected.

4. reforming hydrogen-preparation reactor according to claim 1, which is characterized in that micro- catalysis reaction plate (10) be selected from At least one of surface plate, castellated plates, corrugated plating and corrugated sheet.

5. a kind of reformation hydrogen production reburner, including air inlet pipe (24), escape pipe (25), burner (23) and combustion chamber (22), it is special Sign is that the reburner further includes reforming hydrogen-preparation reactor described in any one of Claims 1 to 4 (21), the reformation Hydrogen-manufacturing reactor (21) is located in the combustion chamber (22), the air inlet (1) of the reforming hydrogen-preparation reactor (21) and it is described into Tracheae (24) connection, the gas outlet (2) of the reforming hydrogen-preparation reactor is connected to the escape pipe (25).

6. the method for carrying out reformation hydrogen production reaction using reformation hydrogen production reburner described in claim 5, which is characterized in that the party Method the following steps are included:

(1) make fuel gas and air spray into the combustion chamber (22) by the burner (23) to burn；

(2) air inlet pipe (24) of unstripped gas and vapor through the reburner is made to enter the reforming hydrogen-preparation reactor (21), Reformation hydrogen production reaction is carried out in the catalysis reaction member (13), obtains the conversion gas rich in hydrogen.

7. according to the method described in claim 6, it is characterized in that, the condition of reformation hydrogen production reaction includes: reaction temperature It is 700~1100 DEG C, reaction pressure is 1.8~5.5MPaG, the H in vapor₂The molar ratio of O and the carbon atom in unstripped gas For (2.5~5): 1, air speed is 1000~100000h^-1。

8. according to the method described in claim 6, it is characterized in that, the unstripped gas is in the catalysis reaction member (13) Mean flow rate is 0.001~100m/s.

9. according to the method described in claim 6, it is characterized in that, the unstripped gas is natural gas, liquefied petroleum gas, refinery At least one of gas, the resolution gas for reforming hydrogen concentrate PSA and naphtha.

10. according to the method described in claim 6, it is characterized in that, the reformation hydrogen production catalysts include reformation hydrogen production Active component, the reformation hydrogen production active component include at least one of nickel, ruthenium, platinum, palladium, iridium and rhodium.