CN209254717U - Micro passage reaction wall and microchannel reaction member - Google Patents

Abstract

This disclosure relates to a kind of micro passage reaction wall and microchannel reaction member, the reactor wall includes: stainless steel basal layer (101), has the first side for forming reaction channel；Coarse machined layer (102) is processed in the first side；And catalyst support layer (103), it is formed on the coarse machined layer (102).Through the above technical solution, the micro passage reaction wall that the disclosure provides is formed by stainless steel basal layer, coarse machined layer and catalyst support layer jointly constructs, catalyst support layer is adhered to by the coarse machined layer being worked on stainless steel basal layer, rather than it is coated on stainless steel basal layer by applying form membrane, coarse machined layer can effectively promote the bond area of catalyst carrier by rough surface, the adhesive force between catalyst support layer and stainless steel basal layer is improved simultaneously, is conducive to reaction and is gone on smoothly.

Description

Micro passage reaction wall and microchannel reaction member

Technical field

This disclosure relates to petroleum refining and chemical reaction Instrument technology field, and in particular, to a kind of micro passage reaction Wall and microchannel reaction member.

Background technique

In recent years, micro passage reaction has become the research hotspot in new reactor field.With in popular response container The chemical reaction of progress is compared, and micro passage reaction has catalyst amount few, and catalyst efficiency is high, spreads, heat transfer short according to rate The advantages that quick, so as to achieve the purpose that accelerate catalysis reaction.

Unevenness in the fixed bed micro passage reaction of common filled type due to catalyst granules accumulation in the reactor Even property and randomness, will lead to catalyst bed has very big pressure drop or causes the bias current of reactant, is unfavorable for catalyst With the utilization of bed；Simultaneously because there are gaps between catalyst and reactor wall, the outside heat transmission resistance of bed can be made to increase.For This, it is more and more to the research of coating type micro passage reaction.Coating type micro passage reaction is mainly by basis material Coating catalyst carrier is reacted to accelerate catalysis, and common basis material has FeCrAl alloy and stainless steel.FeCrAl alloy The disadvantage is that mechanical strength is not high, it is easy to corrode, price is higher.Stainless steel has good heating conduction, shatter-proof ejector half strong and good The advantages that economy got well, but since catalyst carrier and the binding force of stainless steel be not high, cause the catalyst carrier of coating More difficult attachment on stainless steel, and then influences reaction efficiency.

Utility model content

One purpose of the disclosure is to provide a kind of micro passage reaction wall, which can effectively improve The adhesive force of catalyst carrier and stainless steel goes on smoothly catalysis reaction.

Another object of the present disclosure is to provide a kind of microchannel reaction member, which is mentioned by the disclosure The micro passage reaction wall of confession constructs.

To achieve the goals above, the disclosure provides a kind of micro passage reaction wall, and the reactor wall includes: stainless steel Basal layer has the first side for forming reaction channel；Coarse machined layer is processed in the first side；And catalyst Carrier layer is formed in the coarse machined layer.

Optionally, the coarse machined layer is the rough layer formed by sandblasting processing technique.

Optionally, the material spray for forming the sandblasting layer includes quartz sand, copper ore, diamond dust, iron sand or SEMEN AMOMI LONGILIGULA.

Optionally, the particle size range of the material spray is 50 mesh~600 mesh.

Optionally, the roughness of the coarse machined layer is 1 μm -100 μm.

Optionally, the catalyst support layer is alumina layer, and the alumina layer includes being formed on the sandblasting layer Aluminized coating.

Optionally, the alumina layer further includes coated in the alumina sol layer on the aluminized coating.

Optionally, the stainless steel basal layer is plate structure, is formed with plurality of passages slot in the first side, this is more Channel slot is arranged with extending in the same direction.

According to the second aspect of the disclosure, a kind of microchannel reaction member, including above-described microchannel plate are provided Answer wall.

Optionally, the stainless steel basal layer is plate structure, is formed with a plurality of first passage slot in the first side, The a plurality of first passage slot is arranged with extending in the same direction, and the reactor wall is two, and the adjacent reactor wall is right in opposite directions It connects so that the corresponding first passage slot forms the reaction channel.

Optionally, it is welded between the adjacent reactor wall.

Through the above technical solutions, the micro passage reaction wall that the disclosure provides is by stainless steel basal layer, coarse machined layer It is formed with catalyst support layer jointly constructs, catalyst support layer is attached by the coarse machined layer being worked on stainless steel basal layer , rather than be coated on stainless steel basal layer by applying form membrane, coarse machined layer can be promoted effectively by rough surface and be urged The bond area of agent carrier, while the adhesive force between catalyst support layer and stainless steel basal layer is improved, be conducive to react It goes on smoothly.

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 the structural schematic diagram for the micro passage reaction that a kind of illustrative embodiments of the disclosure provide；

Fig. 2 is the main view of Fig. 1；

Fig. 3 is the structural schematic diagram of microchannel reaction member in micro passage reaction shown in fig. 1；

Fig. 4 is the structural schematic diagram of reactor wall in microchannel reaction member shown in Fig. 3；

Fig. 5 is the cross-sectional view of the reactor wall shown in Fig. 4；

Fig. 6 is that the first side docking of two neighboring reactor wall constitutes the structural schematic diagram of reaction channel；

Fig. 7 is that the second side docking of two neighboring reactor wall constitutes the structural schematic diagram of cooling duct.

Description of symbols

11 first passage slot, 12 second channel slot

20 cylindrical bodies 21 adapter tube

30 flange, 101 stainless steel basal layer

102 coarse 103 catalyst support layers of machined layer

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", "lower" are based on Fig. 2 institute The page shown and define, and "inner", "outside" refer to the inner and outer of corresponding component profile.In addition, used in the disclosure Term " first ", " second " etc. are that do not have succession and importance to distinguish an element and another element.Following When description is related to attached drawing, unless otherwise indicated, the same numbers in different drawings indicate the same or similar elements.

Referring to Figure 1 to Figure 7, the disclosure provides a kind of micro passage reaction, including shell and microchannel reaction member.Shell It is exported with feed inlet, discharge port, cooling fluid import and cooling fluid；Microchannel reaction member is located at enclosure interior, and Including micro passage reaction wall.The micro passage reaction wall includes stainless steel basal layer 101, coarse machined layer 102 and catalysis Agent carrier layer 103, stainless steel basal layer 101 have the first side for forming reaction channel, and the coarse processing of machined layer 102 is first On side, catalyst support layer 103 is formed in coarse machined layer 102.Wherein, inlet port and outlet port are connected by reaction channel It is logical, in addition, also having in shell along the cooling duct that microchannel reaction member is arranged, cooling fluid import and cooling fluid outlet It is connected to by cooling duct.

In this way, when the micro passage reaction provided using the disclosure is chemically reacted, reaction raw materials by feed inlet into Enter reaction channel, and the catalyst adhered in the catalyst support layer 103 in the reaction channel being made of reactor wall is urged It is chemically reacted under change effect, final product is discharged by discharge port, and cooling duct can be by internal fluid to anti- Channel is answered to be cooled down.Wherein, the first side of the stainless steel basal layer 101 of reactor wall is formed with reaction channel, and first Coarse machined layer 102 and catalyst support layer 103 are sequentially formed on side, i.e. catalyst support layer 103 is reaction channel Innermost surface, to directly contact and be catalyzed with the raw material entered in reaction channel by catalyst component thereon Reaction.

Itself composed structure of the reactor wall as reactor, internal material tissue includes stainless steel basal layer 101, thick Rough machined layer 102 and catalyst support layer 103.Catalyst support layer 103 as the component part for directly constituting reactor wall, Just already exist in reactor wall formation, rather than to apply form membrane subsequent coated on the stainless steel base of reaction channel, So as to improve the adhesive force and thermal stability between catalyst support layer 103 and stainless steel basal layer 101.That is, Traditional reactor wall is only fabricated by simple stainless steel metal, subsequent to need additionally stainless when being chemically reacted Catalyst is coated in steel matrix, and the reactor wall that the disclosure provides passes through certain mode shape on stainless steel basal layer 101 At having coarse machined layer 102 and catalyst support layer 103, structure construction is significantly different with traditional reactor wall construction, this Structure can effectively improve bond area and adhesive force between catalyst support layer 103 and stainless steel basal layer 101, and urge Agent carrier layer 103 is formed directly on reactor wall, additionally it is possible to make exothermic reaction generate heat quickly conduct or Heat needed for making the endothermic reaction quickly conducts, and is conducive to reaction and goes on smoothly.

Specifically, above-mentioned coarse machined layer 102 can be formed on stainless steel basal layer by various manufacturing process Rough layer, such as in the present embodiment can be the rough layer that is formed by sandblasting processing technique, wherein sandblasting processing technique institute The material spray of selection may include quartz sand, copper ore, diamond dust, iron sand or SEMEN AMOMI LONGILIGULA etc., and the particle size range of material spray can be 50 Mesh~600 mesh.In this way, after sandblasting processing technique rough layer can be formed on stainless steel basal layer.Wherein, blasting craft It uses compressed air that material spray is formed high velocity spray beam for power and is ejected into workpiece surface to be processed, make outer surface of workpiece Variation, impact and shear action due to material spray to workpiece surface, workpiece surface can obtain certain cleannes and different Roughness improves the fatigue resistance of workpiece so that the mechanical performance of workpiece surface and surface property be made to be improved.Corresponding to this Micro passage reaction wall in open, material spray are injected in the first side of stainless steel basal layer 101, Neng Goutong by blasting craft The adhesive force between the rough layer increase stainless steel basal layer 101 formed and catalyst support layer 103 is crossed, catalyst carrier is extended The durability of layer 103, while being also beneficial to wetting and the levelling of catalyst support layer 103.

In other embodiments, coarse machined layer 102 can also pass through other processing hands such as chemical attack, laser-induced thermal etching Section is formed on stainless steel basal layer 101, so that formation rule or irregular matte finish are to improve to catalyst carrier The adhesive force and bond area of layer 103.In addition in some embodiments of the present disclosure, the roughness of the coarse machined layer of formation can Think 1 μm -100 μm.Wherein, roughness is also referred to as surface roughness, which can be indicated with Rz, in some embodiments In, test method are as follows: sample before testing, first with the acetone clear 10min of ultrasound, is then dried up with oil-free compressed air.Using The measurement of TR240 portable surface roughmeter, Rz is the arithmetic of 10 peak valley height of matrix surface (5 peak values add 5 valleies) Average value, sampled point distance can be 0.8mm, and each sample can measure 10 times, and take mean value.

Further, catalyst support layer 103 can be alumina layer, and alumina layer includes being formed in coarse machined layer Aluminized coating.Aluminized coating is prepared by corroding aluminising process, aluminizing medium and the surface of stainless steel basal layer 101 can be made sufficiently to connect Alumina layer obtained is more uniform after touching, aluminising and oxidation, and intensity is more tough and tensile.

Further, alumina layer can also include coated in the alumina sol layer on aluminized coating.Sol-gal process The alumina support of preparation crystal grain after long-term ageing is uniform, well-grown after roasting, porosity with higher, biggish ratio Surface area and suitable aperture, thus there is good heating conduction, thermal stability and higher economy.What is be thusly-formed urges Agent carrier layer 103 can load FT synthetic catalyst component ruthenium by infusion process in some embodiments, in this way can be with Obtaining has excellent FT synthesis performance ruthenium base FT synthetic catalyst.Wherein specific catalytic component can be with according to different reactions Difference, the disclosure are without limitation.

Referring to fig. 4 to fig. 6, above-mentioned stainless steel basal layer 101 can be particularly configured to plate structure, can in first side To be formed with a plurality of first passage slot 11, a plurality of interval of first passage slot 11 is laid, and a plurality of first passage slot 11 is in the same direction Extend, reactor wall can be two, and two adjacent reactor walls dock in opposite directions so that corresponding 11 shape of first passage slot At reaction channel.In the embodiments of the present disclosure, stainless steel basal layer 101 can be stainless steel plate, and first on stainless steel plate is logical Road slot 11 is formed as the reaction channel of micro passage reaction, can be arranged on stainless steel in advance by following methods coarse Machined layer 102 and catalyst support layer 103, can be for example, by prickers per two adjacent reactor walls to form reactor wall The modes such as weldering, High temperature diffusion weldering are fixed together, to form multiple reaction channels in same plane.Wherein, reaction channel is Linear type identical with stainless steel plate extending direction channel, number, size, the spacing in channel can be according to reaction scales and heat release The corresponding setting of amount.In other embodiments, the composition of reaction channel can also be other structures form, such as reaction channel can Directly to be formed by tubular matrix, the form of docking is avoided.

Further, as shown in figure 3, in adjacent microchannel reaction member, cooling duct is formed in stainless steel base layer Between 101 second side, cooling fluid import is exported with cooling fluid and is connected to by cooling duct.First side and second side Face is two opposite end faces of stainless steel basal layer 101, in this way, the two sides of each reactor wall are provided with cooling duct and anti- Channel is answered, so that cooling duct be enable quickly to cool down to reaction channel.

Further, referring to Fig. 4 and Fig. 7, it could be formed with second channel slot 12 in the second side of reactor wall, the One channel slot 11 and second channel slot 12 are arranged in a mutually vertical manner, and in adjacent microchannel reaction member, stainless steel base layer 101 second side docking, so that corresponding second channel slot 12 forms cooling duct.Adjacent stainless steel basal layer 101 Second side can also be fixed together by forms such as welding, in this way, multiple reactor walls, which successively dock, constitutes microchannel plate Answer unit, simultaneous reactions channel and cooling duct stereo staggered arrangement, structure is simple, easily manufactured, and reactor wall can be with It is integrated with reaction channel and cooling duct simultaneously, improves the space utilization rate of micro passage reaction.

In addition, referring to Figures 1 and 2, the shell of micro passage reaction may include the tubular for accommodating microchannel reaction member The both ends of main body 20, cylindrical body 20 can be connected separately with flange 30, to pass through flange 30 for the charging of micro passage reaction Mouth and discharge port are connected with corresponding equipment, and cylindrical body 20 can be fixed with flange 30 by modes such as welding.Wherein, tubular The adapter tube 21 to form cooling fluid import and cooling fluid outlet can be set on the side wall of main body 20, cooling fluid is led to The adapter tube 21 is crossed to be transported in coolant flow channel.

Referring to Fig. 2, microchannel reaction member may include the multiple panel-shaped reactor walls successively docked in assembling, be located at Top layer and undermost reactor wall only can be formed with first passage slot 11 on the first side, and second side can be distinguished It is fixedly connected with upper cover plate and lower cover plate.Wherein, upper cover plate and lower cover plate can be the plate structure with length and width such as reactor walls, Its another end face is connected with the inner wall of cylindrical body 20 respectively.

The disclosure sequentially forms coarse processing to reactor wall combined with specific embodiments below on stainless steel basal layer 101 The step of layer 102 and catalyst support layer 103 and process are described in detail, embodiment that but the present disclosure is not limited thereto.Following In step, initial stainless steel sample is considered as the stainless steel basal layer 101 of reactor wall in the disclosure.

Step 1: stainless steel sample is carried out sand paper polishing, Superficial Foreign Body is removed.Wherein, stainless steel can using 316, The stainless steel of 304 equal series, polishing sand paper can use 100 mesh~600 mesh, it is preferred to use 150 mesh~400 mesh.

Step 2: cleaning oil removing using acetone.By the stainless steel sample after polishing in acetone ultrasonic vibration 10min~ 120min, preferably 30min~60min.After being cleaned using acetone, stainless steel sample is dried, and is dried in air, is done Dry temperature 50 C~300 DEG C.

Step 3: carrying out sandblasting to stainless steel sample surface.Material spray can choose quartz sand, copper ore, diamond dust, iron Sand, SEMEN AMOMI LONGILIGULA etc., preferably quartz sand, 50 mesh of particle size range~600 mesh, preferably 100 mesh~300 mesh.Material spray is with about 0.7MPa's The pressure that pressure sprays to specimen surface is 0.2MPa~3.0MPa, preferably 0.3MPa~1.5MPa, nozzle and surface of test piece method The angle of line be 5 °~45 °, preferably 10 °~15 °, nozzle to test specimen distance be 5mm~150mm, preferably 10mm~ 100mm。

Step 4: stainless steel sample is fitted into batch can, after sample installs, it is full of and is compressed with feed powder is buried, finally with resistance to Chamotte is sealed.

Wherein, bury feed powder be according to mass percent be 1%~15%Al powder, 1%~15%Fe powder, 1%~10%Si Powder, 1%~8%NH4Cl, remaining aluminizing medium being made into for aluminium oxide.In the above aluminizing medium, the mass fraction of Al powder is preferably The mass fraction of 5%~10%, Fe powder is preferably 5%~10%, and the mass fraction of silicon powder is preferably 3%~6%, NH4Cl powder Mass fraction be preferably 2%~4%, remaining is alumina powder.

After fire clay is dry, batch can heat temperature raising in heating furnace.Maturing temperature is 600 DEG C~1200 DEG C, preferably 750 DEG C~1000 DEG C；Heating rate is 0.2 DEG C/min~5.0 DEG C/min, preferably 0.5 DEG C/min~2.0 DEG C/min.By By sample furnace cooling after certain time heat preservation.Soaking time is 30min~1200min, preferably 60min~180min.It is cold But Temperature fall is preferably used.

Step 5: by sample take out and with distilled water flushing it is clean, wash away surface attachment bury feed powder, then in acetone Ultrasonic vibration 10min~120min, preferably 30min~60min.After being cleaned using acetone, stainless steel sample is dried in the air in air It is dry.

Roasting oxidation is carried out step 6: the sample after aluminising is placed in roaster, maturing temperature is 400 DEG C~900 DEG C, Preferably 500 DEG C~700 DEG C；Heating rate is 0.2 DEG C/min~5.0 DEG C/min, preferably 0.5 DEG C/min~3.0 DEG C/min.

Step 7: prepared by alumina sol.

A, the nitric acid that configuration quality score is 0.1%~0.8%, preferably 0.2%~0.5%；By nitric acid and intend thin water Aluminium stone is mixed according to molar ratio H+/Al3+=0.05~0.30, preferably H+/Al3+=0.10~0.20；50 DEG C~ 0.5h~5h, preferably 1h~3h are stirred at 90 DEG C；Then reaction aging 6h~48h, preferably 12h~36h, after obtaining ageing Alumina sol slurries.

B, polyglycol solution is configured.Expanding agent and bonding agent are added, expanding agent and bonding agent are preferably polyethylene glycol.Match Polyglycol solution is set, the mass fraction 5%~40% of polyethylene glycol is made.

C, by after ageing alumina sol slurries and polyglycol solution mix, stir into homogeneous slurry.

Step 8: alumina sol applies.It is coated according to dropwise addition infusion process or dip-coating method.Infusion process, which is added dropwise, is Alumina sol slurries are added drop-wise on sample, the wellability of enhancing alumina layer is generated by stainless steel surface, realize oxidation Aluminum sol slurries are sprawled specimen surface；Dip-coating method is impregnated in sample in alumina sol slurries, is then taken out Sample drains sample.It is preferred that infusion process is added dropwise.

Step 9: after the completion of coating, it is sufficiently dry at room temperature, then at 50 DEG C~300 DEG C, preferably 100 DEG C~150 DEG C It is dry；Time is 0.5h~10h, preferably 2h~4h；0.05 DEG C/min~5.0 DEG C of heating rate/min, preferably 0.1 DEG C/ Min~3.0 DEG C/min.

Step 10: coating sample coupon can be put into Muffle kiln roasting after dry, maturing temperature is 450 DEG C~900 DEG C, is risen Warm rate is 0.2 DEG C/min~5.0 DEG C/min, preferably 0.5 DEG C/min~3.0 DEG C/min.Time is 0.5h~10h, preferably For 2h~4h；Cooled to room temperature takes out sample.

Step 11: repetitive coatings repeatedly can be improved load capacity as needed, preferably 1 time~5 times.

In above-mentioned steps, third step is that coarse machined layer is arranged in the first side of stainless steel basal layer 101, the 4th Step to the 6th step is that aluminized coating is arranged in coarse machined layer, is the setting alumina sol layer on aluminized coating after the 7th step. Wherein, the method for the coarse machined layer of formation and catalyst support layer 103 that use is routine side well known to those skilled in the art Method, specific process parameter value can also be adjusted accordingly and be set according to realization situation.

The reactor wall formed by the above method, stainless steel basal layer 101 and catalyst support layer 103 pass through coarse Machined layer 102 is effectively attached together, and is improved the adhesive force and bond area of catalyst carrier on stainless steel, is made to chemically react It is smooth.The beneficial effect that reactor wall has can further be embodied by following comparative example and embodiment.

Comparative example 1

Test specimen (3.0mmX3.0mm) is handled first.Surface surpasses in acetone soln after the polishing of 500 mesh sand paper Sound wave shock 30min removes surface smut.According to 7%Al powder, 7%Fe powder, 3%Si powder, 3%NH4Cl, remaining be aluminium oxide It is made into aluminizing medium.Aluminizing medium and test specimen are mixed, roast 120min at 900 DEG C, surface is made rich in the stainless of aluminium Steel.The surface of test specimen is cleaned after the completion of aluminising, then the ultrasonic oscillation 45min in acetone soln, removal surface is dirty Dirt is warming up to 600 DEG C of roasting 120min with the heating rate of 2.0 DEG C/min, prepares the stainless steel that surface is rich in alumina layer Piece.Nitric acid and boehmite are mixed according to molar ratio H+/Al3+=0.10, after stirring 1.0h at 80 DEG C, reaction It is aged 12h, the alumina sol after being aged；Colloidal sol and 20% polyethylene glycol mixing, homogeneous slurry is stirred into, according to Infusion process is added dropwise to be applied.After the completion of coating, 3h is dried at room temperature, then in 120 DEG C of dry 3h, 0.5 DEG C of heating rate/ min.Coating part can be put into Muffle kiln roasting after drying, and maturing temperature is 600 DEG C, and heating rate is 0.8 DEG C/min, time For 3h, cooled to room temperature takes out sample.It is denoted as DB01.

Embodiment 1

Test specimen (3.0mmX3.0mm) is handled first.Surface surpasses in acetone soln after the polishing of 500 mesh sand paper Sound wave shock 30min removes surface smut.Blasting treatment is carried out to stainless steel sample surface, to form coarse machined layer.Material spray It can choose quartz sand, particle size range: 200 mesh~300 mesh.According to 7%Al powder, 7%Fe powder, 3%Si powder, 3%NH4Cl, its It is remaining to be made into aluminizing medium for aluminium oxide.Aluminizing medium and test specimen are mixed, roast 120min at 900 DEG C, surface richness is made Stainless steel containing aluminium.The surface of test specimen is cleaned after the completion of aluminising, then the ultrasonic oscillation 45min in acetone soln, Surface smut is removed, 600 DEG C of roasting 120min are warming up to the heating rate of 2.0 DEG C/min, prepares surface rich in aluminium oxide The stainless steel substrates of layer.Nitric acid and boehmite are mixed according to molar ratio H+/Al3+=0.10, stirred at 80 DEG C After 1.0h, reaction aging 12h, the alumina sol after being aged；Colloidal sol and 20% polyethylene glycol mixing, stir into Homogenate is applied according to infusion process is added dropwise.After the completion of coating, 3h is dried at room temperature, then in 120 DEG C of dry 3h, heating 0.5 DEG C/min of rate.Coating part can be put into Muffle kiln roasting after drying, and maturing temperature is 600 DEG C, heating rate 0.8 DEG C/min, time 3h, cooled to room temperature taking-up sample.It is denoted as A01.

Embodiment 2

Test specimen (3.0mmX3.0mm) is handled first.Surface surpasses in acetone soln after the polishing of 400 mesh sand paper Sound wave shock 30min removes surface smut.Blasting treatment is carried out to stainless steel sample surface, to form coarse machined layer.Material spray It can choose quartz sand, particle size range: 200 mesh~300 mesh.According to 8%Al powder, 5%Fe powder, 3%NH4Cl, remaining for oxidation Aluminium is made into aluminizing medium.Aluminizing medium and test specimen are mixed, roast 120min at 850 DEG C, surface is made and is rich in aluminium not Become rusty steel.The surface of test specimen is cleaned after the completion of aluminising, then the ultrasonic oscillation 45min in acetone soln, removes surface Dirt is warming up to 500 DEG C of roasting 120min with the heating rate of 2.0 DEG C/min, prepares the rich salic stainless steel in surface Piece.Nitric acid and boehmite are mixed according to molar ratio H+/Al3+=0.12, after stirring 1.0h at 70 DEG C, reaction It is aged 12h, the alumina sol after being aged；Colloidal sol and 20% polyethylene glycol mixing, homogeneous slurry is stirred into, according to Infusion process is added dropwise to be applied.After the completion of coating, 3h is dried at room temperature, then in 120 DEG C of dry 3h, 0.5 DEG C of heating rate/ min.Coating part can be put into Muffle kiln roasting after drying, and maturing temperature is 700 DEG C, and heating rate is 0.8 DEG C/min, time For 3h, cooled to room temperature takes out sample.It is denoted as A02.

Embodiment 3

Test specimen (3.0mmX3.0mm) is handled first.Surface surpasses in acetone soln after the polishing of 400 mesh sand paper Sound wave shock 30min removes surface smut.Blasting treatment is carried out to stainless steel sample surface, to form coarse machined layer.Material spray It can choose quartz sand, particle size range: 200 mesh~300 mesh.According to 9%Al powder, 4%Fe powder, 4%NH4Cl, remaining for oxidation Aluminium is made into aluminizing medium.Aluminizing medium and test specimen are mixed, roast 120min at 900 DEG C, surface is made and is rich in aluminium not Become rusty steel.The surface of test specimen is cleaned after the completion of aluminising, then the ultrasonic oscillation 45min in acetone soln, removes surface Dirt is warming up to 500 DEG C of roasting 120min with the heating rate of 2.0 DEG C/min, prepares the rich salic stainless steel in surface Piece.Nitric acid and boehmite are mixed according to molar ratio H+/Al3+=0.15, after stirring 1.0h at 70 DEG C, reaction It is aged for 24 hours, the alumina sol after being aged；Colloidal sol and 25% polyethylene glycol mixing, homogeneous slurry is stirred into, according to Infusion process is added dropwise to be applied.After the completion of coating, 3h is dried at room temperature, then in 120 DEG C of dry 3h, 0.5 DEG C of heating rate/ min.Coating part can be put into Muffle kiln roasting after drying, and maturing temperature is 800 DEG C, and heating rate is 0.8 DEG C/min, time For 3h, cooled to room temperature takes out sample.It is denoted as A03.

Before applying alumina sol and after coating alumina sol calcination process, the quality of sample is measured respectively, Calculate the gain in weight of sample.Ultrasonic vibration 15min is carried out in distilled water.Then in 300 DEG C of dryings.Measure catalyst carrier oxygen Change the expulsion rate of aluminium.Obtain following numerical value:

Specimen coding	Sample weight gain/g	Lose expulsion rate/%
			DB01	0.112	9.4%
A01	0.124	5.2%
			A02	0.131	4.6%
A03	0.123	4.7%

Comparison DB01 and A01 is it is found that by sequentially forming coarse machined layer 102 and catalysis on stainless steel basal layer 101 Agent carrier layer 103, adhesion amount of the catalyst support layer 103 on stainless steel basal layer 101 increase, and not easy to fall off, i.e., Adhesive force between catalyst support layer 103 and stainless steel basal layer 101 improves.A01, A02, A03 are compared it is found that in catalyst In the forming process of carrier layer 103, the process parameter value in preferred scope provided using the disclosure equally can be mentioned further Adhesive force of the high catalyst carrier layer 103 on stainless steel basal layer 101.

In addition, supported active metals component can be continued in the catalyst support layer 103 of above-mentioned reactor wall, with system The standby synthetic catalyst for being applied to different chemical reactions, keeps reaction more efficient.Citing is illustrated below, but the model of the disclosure It encloses and is not limited thereto, in the case where not departing from disclosure central scope, other modes of texturing also fall into the scope of the present disclosure It is interior.

Fischer-Tropsch synthesis (FT reaction) is a strongly exothermic gas-solid-liquid multiphase reaction system, in fixed bed reactors In, the particle diameter of catalyst is generally several millimeters, and therefore, influence of the diffusion control to catalytic activity is difficult to avoid that.And by The heavy paraffinic waxes that F- T synthesis obtains usually are supported on catalyst surface in the form of liquid, vapour colloidal sol or slurry, to reactant H₂ It is had an impact with diffusion of the CO inside catalyst granules.In the interior diffusion process of reactant, H₂Diffusion velocity ratio CO it is fast, CO is significantly stronger than H in the diffusion restriction effect of catalyst particles intragranular₂.Because the partial size of particle is different, it is dense to result in CO inside particle The difference for spending gradient, affects the combination of CO and metal active centres position, so that the H/C ratio adsorbed on activated centre increases, Carbon chain growth probability reduces, and reduces the selectivity of C5+.Solve the problems, such as this effective way first is that improve FT synthesis catalytic FT synthetic catalyst is supported in metallic walls by the mode of loading of agent, and the heat for reacting generation can be spread out of by metallic conductor, solution Certainly strongly exothermic problem；It is supported on the thin layer catalyst in metallic walls simultaneously since diffusion length is short, to raising C5+ hydrocarbon selective Also advantageous, diffusion can also smoothly make reaction more efficient.

It in one embodiment, can supported active metals component Co, formation in above-mentioned catalyst support layer 103 Aluminum oxide coating layer Co base FT synthesis catalytic oxidant layer, specific operation process are to continue following step after the 11st above-mentioned step Suddenly.

Step 12: supported active metals Co.

A, the content of metal component Co is counted by oxide and on the basis of catalyst, and preferred active metal component contains Amount is 5~80 weight %, and further preferably 10~70 weight % are more preferably 20~60 weight %.

B, the compound of the Co containing active metal component is selected from these their one or more of soluble compounds, example It such as can be one or more of cobalt nitrate, cobalt acetate, cobalt carbonate, cobalt chloride, soluble complexes.

C, the salt of the active component Co of catalyst can be introduced using conventional method, it is preferred to use the method for dipping is to urging Active metal component is introduced in agent carrier, dipping method is conventional method, such as prepares the compound containing active metal component Solution, later by impregnating or the method for spray dipping, dry and roast.

D, the auxiliary agent in catalyst is selected from Cu, Mo, Ta, W, Ru, Zr, Ti, REO, Re, Hf, La, Ce, Mn, V and noble metal One or more of adjuvant component, one or more of auxiliary agent preferred W, Zr, Re, Ru, Ce therein, noble metal therein It is the auxiliary agent group for being usually used in fischer-tropsch synthetic catalyst known to FT synthesis field selected from one or more of Pt, Pd, Rh, Ir Point.According to the catalyst support layer that the disclosure provides, it optionally can optionally contain and be selected from one of above-mentioned adjuvant component or several Kind.

E, auxiliary agent is counted and on the basis of catalyst in addition to noble metal by oxide, and the content of adjuvant component is preferably 30 Weight % hereinafter, further preferably 20 weight % hereinafter, more preferably 15 weight % or less.

F, it when adjuvant component is selected from noble metal, is counted by metal and on the basis of catalyst, the content of adjuvant component is preferred In 10 weight % hereinafter, further preferably 1 weight % or less.Adjuvant component can before supported active metals component, it It introduces afterwards or simultaneously, wherein it is preferred that the method impregnated before or while carried metal component introduces.

Step 13: catalyst is dry, dry temperature can be 50 DEG C -200 DEG C, preferably 100 DEG C~180 DEG C, more Preferably 120 DEG C~150 DEG C.

Step 14: catalyst roasts, the temperature of roasting can be 200 DEG C -600 DEG C, preferably 250 DEG C~600 DEG C, roast The burning time is 1~12h, preferably 2~6h.

Step 15: repeated impregnations repeatedly can be improved the load capacity of active component Co as needed, preferably 1 time~5 times.

The reactor wall with aluminum oxide coating layer Co base FT synthesis catalytic oxidant layer of above-mentioned formation is assembled into reactor, it should Reactor is applied to FT synthetic reaction, wherein FT synthetic reaction condition is the popular response condition of FT synthetic reaction.For example, pressing According to the conventional method in this field, first by catalyst reduction, suitable reducing condition includes: that reduction temperature is 100 DEG C to 800 DEG C, preferably 200 DEG C to 600 DEG C, further preferably 300 DEG C to 450 DEG C；Recovery time be 0.5~72h, preferably 1~ For 24 hours, further preferably 2~8h, reduction can carry out in pure hydrogen, can also carry out in the gaseous mixture of hydrogen and inert gas, It is such as carried out in hydrogen with the gaseous mixture of nitrogen and/or argon gas, Hydrogen Vapor Pressure is 0.1~4MPa, preferably 0.1~2MPa.

It further, can be with by the mixture of carbon monoxide and hydrogen and the catalytic condition of catalyst are as follows: preferred temperature Degree is 160 DEG C~300 DEG C, and further preferably 190 DEG C~250 DEG C, pressure is preferably 1~8MPa, further preferably 1- The molar ratio of 5MPa, hydrogen and carbon monoxide is 0.4~2.5, preferably 1.5~2.5, further preferably 1.8~2.2, gas The when null-rate of body is 2000~300000h-1, preferably 4000~200000h-1.

The disclosure is continued with comparative example and embodiment to being formed with aluminum oxide coating layer Co base FT synthesis catalytic oxidant layer The beneficial effect of reactor wall is illustrated.

Specifically, carrier A01, A02 and A03 obtained in above-mentioned comparative example and embodiment and comparison vehicle DB01 are used Mixed solution containing cobalt nitrate and auxiliary agent carries out saturation dipping, is dried and roasts later, obtain catalyst C01, C02 and C03 and comparative catalyst CDB01.Wherein, drying temperature is 120 DEG C, and drying time is 3 hours, and maturing temperature is 350 DEG C, Calcining time 3 hours.The dosage of cobalt nitrate contains 45~50 weight % of cobalt oxide content, precious metal additive in final catalyst Amount is about 0.1 weight %Pt.

The FT for evaluating catalyst C01, C02 and C03 and comparative catalyst CDB01 respectively in fixed bed reactors is closed At reactivity worth.The stainless steel substrates of load active component are mounted in the slit of inside reactor.Unstripped gas composition: H2/CO/N2 =64%/32%/4% (hundred number of volume).

Catalyst reduction reaction condition: pressure is normal pressure, and heating rate is 5 DEG C/min, hydrogen gas space velocity 2000h-1, is gone back Former temperature is 400 DEG C, recovery time 5h.

Reaction condition: pressure 3.0MPa, 220 DEG C of temperature, synthesis gas (unstripped gas) air speed 10000h-1.

Reaction takes gas sample to carry out chromatography after carrying out 24 hours, wherein conversion ratio, methane selectively and the C5+ of CO Hydrocarbon selective is listed in the table below.

As seen from the above table, it is chemically reacted using the reactor wall that the disclosure provides, FT synthesis catalytic oxidant layer, which has, lives Property it is high, C5+ hydrocarbon selective is high, the low feature of methane selectively, is better than prior art comparative example.

In other embodiments, can also in above-mentioned catalyst support layer 103 supported active metals component Ru, system Standby aluminum oxide coating layer Ru base FT synthetic catalyst, or the load active component Ni in above-mentioned catalyst support layer 103, preparation SMR catalyst for methane-steam reforming (SMR reaction).Wherein, preparation method and technology parameter is this field skill Conventional method known to art person is not done excessively repeat here.

In conclusion the micro passage reaction that the disclosure provides has by stainless steel basal layer 101, coarse machined layer 102 And the micro passage reaction wall that catalyst support layer 103 collectively forms, chemical reaction is carried out using the reactor, can effectively be mentioned Adhesive force and bond area between high catalyst carrier layer 103 and stainless steel basal layer 101, and catalyst support layer 103 It is formed directly on reactor wall, additionally it is possible to which the heat for generating exothermic reaction quickly conducts or makes needed for the endothermic reaction Heat quickly conduct, be conducive to reaction go on smoothly.

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, 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 (10)

1. a kind of micro passage reaction wall, which is characterized in that the reactor wall includes:

Stainless steel basal layer (101) has the first side for forming reaction channel；

Coarse machined layer (102) is processed in the first side；And

Catalyst support layer (103) is formed on the coarse machined layer (102).

2. micro passage reaction wall according to claim 1, which is characterized in that the coarse machined layer (102) is to pass through The rough layer that sandblasting processing technique is formed.

3. micro passage reaction wall according to claim 2, which is characterized in that the material spray of the sandblasting processing process selection Including quartz sand, copper ore, diamond dust, iron sand or SEMEN AMOMI LONGILIGULA, the particle size range of the material spray is 50 mesh~600 mesh.

4. micro passage reaction wall according to claim 1, which is characterized in that the roughness of the coarse machined layer is 1 μ m-100μm。

5. micro passage reaction wall described in any one of -4 according to claim 1, which is characterized in that the catalyst carrier Layer (103) is alumina layer, and the alumina layer includes the aluminized coating being formed in the coarse machined layer.

6. micro passage reaction wall according to claim 5, which is characterized in that the alumina layer further includes being coated in institute State the alumina sol layer on aluminized coating.

7. micro passage reaction wall according to claim 1, which is characterized in that the stainless steel basal layer (101) is plate Shape structure is formed with plurality of passages slot in the first side, which is arranged with extending in the same direction.

8. a kind of microchannel reaction member, which is characterized in that including microchannel described according to claim 1 any one of -6 Reactor wall.

9. microchannel reaction member according to claim 8, which is characterized in that the stainless steel basal layer (101) is plate Shape structure is formed with a plurality of first passage slot (11) in the first side, which extends in the same direction ground Setting, and the reactor wall is two, and the adjacent reactor wall docks in opposite directions so that the corresponding first passage Slot (11) forms the reaction channel.

10. microchannel reaction member according to claim 9, which is characterized in that welded between the adjacent reactor wall It connects.