CN106732595A - High-specific surface area integral alumina copper-loading catalyst - Google Patents
High-specific surface area integral alumina copper-loading catalyst Download PDFInfo
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- CN106732595A CN106732595A CN201710041564.3A CN201710041564A CN106732595A CN 106732595 A CN106732595 A CN 106732595A CN 201710041564 A CN201710041564 A CN 201710041564A CN 106732595 A CN106732595 A CN 106732595A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
- B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
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Abstract
The invention belongs to catalysis technical field, it is related to a kind of high-specific surface area integral alumina copper-loading catalyst, comprising method for preparing catalyst and catalyst prod feature.Wherein preparation method uses the following raw material：Aluminum precursor, copper precursors, the first additive, the second additive, acid solution；Use integral catalyzer mould；By above-mentioned raw materials and mould, its preparation process is comprised the steps of：First, molding precursor is prepared；2nd, the assembling of molding precursor and mould；3rd, pressure is applied to molding precursor；4th, the program roasting of formed blocks.The product of above-mentioned preparation method possesses following product feature：The block quality of single integral alumina copper-loading catalyst is up to 1 ~ 100 g；Specific surface area is higher；Copper mass content in single catalyst block is up to 1 ~ 20 %；The X ray diffraction peaks of catalyst only wrap salic SPECTROSCOPIC CHARACTERIZATION, and are free of the SPECTROSCOPIC CHARACTERIZATION on copper component.
Description
Technical field
The invention belongs to catalysis technical field, be related to a kind of high-specific surface area integral alumina copper-loading catalyst and its
Preparation method, in particular it relates to a kind of is with the whole of high-specific surface area with alumina precursor moulded pottery not yet put in a kiln to bake one-shot forming by copper precursors
Body formula alumina load copper catalyst and preparation method thereof.
Background technology
Catalyst is closely related with industrial production.Common catalyst activity component in chemical products, energy carrier production
Mostly transition metal component.Wherein period 1 transition metal is abundant and cheap due to its, in actual applications often by people's emphasis
Concern.Copper-based catalysts are industrial conventional catalyst, and it is usually used in methanol-fueled CLC, and oxidation of alcohols, the dehydration of polyalcohol is more
Numerous chemical process with economic worth such as the hydrogenation deoxidation of first alcohol.Copper-based catalysts are also possible to can serve as absorption
Agent, it has more prominent performance for the adsorbing and removing of sulfur-containing compound, ammonia nitrogen compound.Numerous researchs show, even if
For same catalytic active component, the preparation method of solid catalyst can also significantly affect this its catalytic performance.Therefore originally
Field need researcher constantly explore improvement solid catalyst preparation technology, and technique variation.From this angle
See, for particle or copper powder catalyst, currently for integral supported type copper catalyst preparation method also not
Many, especially whole block is all the situation of copper catalyst.But from principle, integral catalyzer is relative to powder or particle
There are some advantages of itself for shape catalyst.For example, the former with the latter is compared, its catalyst filling and the side of comparing is reclaimed
Just, running cost is substantially reduced, especially the separation costs of catalyst and product；For in fixed bed reactors, the former to be often
With less pressure drop.Therefore the preparation method for developing integral supported type copper catalyst has important potential using value.
By the document of the reports such as Henan coal industry Chemical Group research institute seedling outstanding person【Macroporous structure is to CO preferential oxidation monoblock types
CuO-CeO2/α-Al2O3The influence of catalysis activity, petrochemical industry, volume 2011,40,9 phases, page 932】In describe a kind of aluminum oxide
The preparation method of supported copper base monolithic catalyst.For the preparation of carrying alumina body portion, the method passes through water-oil phase system
Standby polystyrene emulsion then aggregates into polystyrene moulding, and Alumina gel is filled into polystyrene moulding afterwards, passes through
1300 oC high-temperature roastings removing template obtains alumina support.Final catalyst is then obtained by equi-volume impregnating.The party
The total production procedure of method is more complicated, and flow is more long.Meanwhile, the document does not disclose the data in terms of specific surface area.From
Seen in principle, by 1300oα-the Al that C high-temperature roastings are obtained2O3Carrier surface area is smaller.
The document of Dan Xuelei et al. reports【The NO of the Cu-ZSM-5/ cordierite monolithic catalysts of different silica alumina ratios is decomposed
Reactivity worth, is catalyzed journal, volume 2001,22,3 phases, page 242；The H of cupric MFI molecular sieves2- TPR and O2- TPD is studied, and catalysis is learned
Report, volume 2001,22,3 phases, page 238】In provide a kind of ZSM-5 molecular sieve of supported copper and be attached to method on cordierite.
The method first prepares Cu-ZSM-5 molecular sieves using ion-exchange, and then the molecular sieve is deposited by way of static crystallization
Onto cordierite.The document does not disclose the data in terms of specific surface area yet.Speculate from principle, although Cu-ZSM-5's
Specific surface area is larger, but because cordierite occupies major part in overall catalysis material, and its surface area is very low, thus it is overall
The surface area of upper catalyst should not be high.
For the preparation of integral supported copper catalyst, also there is the skill of this improvement preparation method in this area
Art demand, especially prepares high-specific surface area, high-copper component decentralization, the demand of the process of low cost operation.
The content of the invention
In order to overcome the problems of prior art, the present invention to propose a kind of first making alumina precursor and copper precursors
Mixing precursor moulded pottery not yet put in a kiln to bake, and by mould compression forming, the technology path of product is then obtained by the roasting of fine program.It is logical
Cross the technology path can obtain high-specific surface area, it is microcosmic on possess nanoscale duct integral alumina load copper catalysis
Agent；The preparation method is relatively low without expensive device, simple raw material sources, more friendly environment, safe operation, cost simultaneously.
Realizing the concrete technical scheme of above-mentioned technology path is：
A kind of high-specific surface area integral alumina copper-loading catalyst, comprising integral alumina copper-loading catalyst preparation side
Method and integral alumina copper-loading catalyst product feature；Wherein preparation method uses the following raw material：
Aluminum precursor：One kind of aluminium hydroxide, boehmite, or above-mentioned substance arbitrary proportion mixture；
Copper precursors：It is copper nitrate, copper chloride, copper bromide, copper sulphate, copper carbonate, basic copper carbonate, acetylacetone copper, ethylenediamine
One kind in tetraacethyl copper, copper acetate, cupric oxalate, Kocide SD, or above-mentioned substance arbitrary proportion mixture；
First additive：It is sesbania powder, sesbania gum, guar gum, cation guar gum, sodium alginate, carboxymethylcellulose calcium, carboxylic second
One kind in base cellulose, sodium carboxymethylcellulose, sodium hydroxyethlcellulose, galactomannans, or above-mentioned substance is any
The mixture of ratio；
Second additive：Be ethanol, propyl alcohol, butanol, ethylene glycol, propane diols, polyethylene glycol, polyvinyl alcohol, glucose, fructose,
Sucrose, maltose, cellobiose, granularity are less than the carbon black of 60 mesh, granularity less than the one kind in the water soluble starch of 60 mesh,
Or the mixture of above-mentioned substance arbitrary proportion；
Acid solution：A kind of aqueous solution, contains nitric acid, sulfuric acid, hydrochloric acid, acetic acid, oxalic acid, phosphoric acid, citric acid, maleic acid, tartaric acid
In one or more materials, the pH value of the aqueous solution is in the range of 0.0 ~ 4.0.
The preparation method of above-mentioned integral alumina copper-loading catalyst, uses integral catalyzer mould；This into
Pattern tool includes the part of mould first, the part of mould second and the part of mould the 3rd；The part of mould first includes a cylinder
Cavity；The part of mould second includes mould the second part crimping section and mould the second part pressure-bearing part；The part of mould second
The geometry of crimping section is cylinder, and it has a compressive plane, and the geometry of the compressive plane is circle；Mould second
Part pressure-bearing part has a pressure-bearing surface；The part of mould the 3rd includes the part crimping section of mould the 3rd and the part of mould the 3rd
Pressure-bearing part；The geometry of the part crimping section of mould the 3rd is cylinder, and it has a compressive plane, the compressive plane it is several
What is shaped as circle；The part pressure-bearing part of mould the 3rd has a pressure-bearing surface；The compressive plane of mould the second part crimping section
The axis direction of the cylindrical cavity that can be included from the part of mould first with the compressive plane of the part crimping section of mould the 3rd is put
Enter.
The preparation method of above-mentioned integral alumina copper-loading catalyst, by above-mentioned raw materials and integral catalyzer into
Pattern has, and its preparation process is comprised the steps of：
Step one, prepare molding precursor；
The assembling of step 2, molding precursor and mould；
Step 3, to molding precursor apply pressure；
Step 4, the roasting of the program of formed blocks.
The specific method of aforementioned four step is as follows：
Step one, prepare molding precursor；Specific method is as follows：
Take aluminum precursor, copper precursors, the first additive, second additive of certain mass；Rubbing containing copper wherein in copper precursors
The ratio between molal quantity containing aluminium element is 0.005 ~ 0.15 in that number and aluminum precursor；The quality of the first additive is aluminum precursor quality
0.01 ~ 0.1 times；The quality of the second additive is 0 ~ 0.2 times of aluminum precursor quality；Four kinds of materials uniformly mix, and obtain mixed powder
End；Acid solution is then poured slowly into mixed-powder, dough is formed, the quality of wherein acid solution is aluminum precursor quality
0.5 ~ 1.3 times；Kneading is carried out to dough by hand or banded extruder so that aluminum precursor therein, the first addition
Thing, the second additive, acid solution further uniformly mix, and form a moulded pottery not yet put in a kiln to bake, do not have obvious drop on moulded pottery not yet put in a kiln to bake；By above-mentioned mixed
The moulded pottery not yet put in a kiln to bake that compound kneading is obtained referred to as molding precursor.
The assembling of step 2, molding precursor and mould；Specific method is as follows：
Molding precursor is filled in the cylindrical cavity that the part of mould first of integral catalyzer mould is included, into
The quality of type precursor is in 2 ~ 400 g ranges；By mould the second part crimping section and the part crimping section of mould the 3rd from
The both sides of the cylindrical cavity that the part of mould first is included are respectively charged into；Molding precursor, mould the second part crimping section with
The order that the part crimping section of mould the 3rd loads the cylindrical cavity that the part of mould first is included is not limited；When mould the 2nd 0
The cylindrical empty that the compressive plane of part crimping section, the compressive plane of the part crimping section of mould the 3rd and the part of mould first are included
Cavity wall is collectively forming an airtight cavity, and above-mentioned molding precursor is enclosed in the airtight cavity, completes number of assembling steps.
Step 3, to molding precursor apply pressure；Specific method is as follows：
The molding precursor that will be assembled is combined with integral catalyzer mould and is placed on a hydraulic press, the part of mould second
The pressure-bearing surface of pressure-bearing part, the pressure-bearing surface of the part pressure-bearing part of mould the 3rd are contacted with the applying press member of hydraulic press so that
Hydraulic press pressure applied can act on above-mentioned two pressure-bearing surface；The pressure size of applying is in the range of 0.1 ~ 5 MPa；
Applying pressure time is in the range of 20 s ~ 4 h；The molding precursor after being pressurized then is taken out from mould to be molded
Block.
Step 4, the roasting of the program of formed blocks；Specific method is as follows：
Operation is dried to formed blocks described in step 3, part volatility moisture is left formed blocks with other materials,
Until the dried quality of formed blocks is less than 75% before drying；Drying process including but not limited to drying, dry in atmosphere
Drying in case or Muffle furnace, dry in vacuum drying chamber, dry in drier, blowing drying, daylight is dried, infrared lamp is dried,
The operations such as centrifuge drying, or any combination of aforesaid operations is operated；Formed blocks are placed in into one afterwards has temperature programmed control
It is calcined in the heater of function；The atmosphere of roasting is air, or purity oxygen, or any oxygenous ratio is mixed more than 20%
Close gas；Temperature and time relation in program roasting includes three temperature controlling stages, is referred to as the first temperature control stage, the
Two temperature control stages and the 3rd temperature control stage；First temperature control stage had an initial temperature, and its value is 20 ~ 150oIn the range of C
Certain value, with a final temperature, its value is 300 ~ 750oCertain value in the range of C；First temperature control stage is from starting
Temperature is to final temperature average ramp rate 0.5 ~ 8oIn the range of C/min；The total time of the first temperature controlling stages exists
In the range of 30 min ~ 12 h；Second temperature control stage had an initial temperature, and its value is 300 ~ 750oCertain in the range of C
Individual value, with a final temperature, its value is also 300 ~ 750oCertain value in the range of C；Second temperature control stage is warm from starting
Final temperature average ramp rate is spent -2 ~ 2oIn the range of C/min；The total time in the second temperature control stage is in 1 ~ 6 h
In the range of；3rd temperature control stage had an initial temperature, and its value is 300 ~ 750oCertain value in the range of C, with one
Final temperature, its value is 20 ~ 150oCertain value in the range of C；3rd temperature control stage is average from initial temperature to final temperature
Rate of temperature change is -8 ~ -0.5oIn the range of C/min；The total time in the 3rd temperature control stage is in the range of 2 ~ 24 h.
Complete after step 4, formed blocks are converted into final products integral alumina copper-loading catalyst；Prepared
Journey is completed.
By the sign to above-mentioned final products, the product of above-mentioned preparation method, integral alumina copper-loading catalyst,
Also it is provided simultaneously with following product feature：
（1）The block quality of single integral alumina copper-loading catalyst is up to 1 ~ 100 g；
（2）The specific surface area of integral alumina copper-loading catalyst is 150 ~ 550 m2/g；
（3）Copper mass content in single integral alumina copper-loading catalyst block is up to 1 ~ 20 %；
（4）The X-ray diffraction peak of integral alumina copper-loading catalyst only wraps salic SPECTROSCOPIC CHARACTERIZATION, and is free of pass
In the SPECTROSCOPIC CHARACTERIZATION of copper component.
Because the X-ray diffraction peak SPECTROSCOPIC CHARACTERIZATION of aluminum oxide is known to those skilled in the art, therefore the present invention need not be given.
It is above-mentioned（3）、（4）2 points of comprehensive explanations, while with considerable copper component load capacity, copper component has on microcosmic
There is decentralization very high.It is noted that the characterization test method of the present invention and non-protected product, but the protection present invention is obtained
The due feature of product.Characterization test method used by this product is all method that those skilled in the art commonly use.
In above-mentioned relevant second additive, the representation of " 60 mesh " that moieties contain, used this area for
A kind of idiomatic expression method of grain or powdered solid substance particle size.In the art, " mesh number " represents a tool
There is the grid number contained by the screen cloth per inch for being uniformly distributed co-ordination.Certain particle can illustrate this by such screen cloth
Particle size is less than the size of the defined of related mesh number.For example, a screen cloth for 60 mesh, if having being uniformly distributed co-ordination,
The grid number that each inch contains is 60；If certain particle can be can be expressed as the particle size and be less than by such screen cloth
60 mesh, specifically, size is less than 1 inch/60=2.54 cm/60=0.0423 cm.
Hydraulic press is the usual means in industry and laboratory research, refers to one kind with liquid as working media, is used for
Energy or pressure is transmitted to realize polytechnic machine.The present invention realizes applying one to being extruded object both sides using hydraulic press
Fixed pressure, the particular type specification for hydraulic press does not do any limitation.
" operation is dried to formed blocks described in step 3 " in for above-mentioned steps four, it should be noted that in ability
In domain or even in various fields, it is a kind of common routine that the solid matter of moisture content or other volatile materials is dried
Operation.The basic object of drying process is part or all of moisture or other volatile materials is left solid.Usual solids
Matter is dried, and in addition to being placed in and being dried naturally in air, can also be dried up using hair-dryer, oven for drying, and infrared lamp dries
Dry, the sun is dried, vacuum drying chamber drying, is placed in drier and the operating method such as is dried, or aforesaid operations is any
Combination operation.Therefore, if be dried to formed blocks using above-mentioned any one operation or various operative combinations so that
The dried mass ratio of formed blocks is reduced to 75% or less before drying, and equivalence operation is belonged in the present invention.
" having the heater of temperature programmed control function " described in above-mentioned steps four is catalyst, solid material preparation field
In commonly use a kind of equipment, i.e., the Temperature-time relation that its temperature that can be realized in a heater is previously set according to certain
Curvilinear motion；The concrete form freedom of heater, can be but not limited to tube furnace, Muffle furnace, baking oven, electric furnace etc..
Average ramp rate is defined as follows in above-mentioned steps four：If in certain moment t1When thermometric object temperature value
It is T1, in another moment t2When thermometric object temperature value be T2, wherein t2In t1Afterwards, then from t1To t2This period
Interior, average ramp rate can be expressed as the business of temperature change value and time change value, i.e. (T2-T1)/(t2-t1).If warm
Degree is with Celsius' thermometric scaleoC or thermodynamic scale K is unit, and the time, the unit of average ramp rate was in units of minoC/
Min or K/min.HereoC/min is identical with the value of K/min.It is clear that also having other normal due to temperature and time
With unit, those skilled in the art can voluntarily carry out the conversion of unit.
" specific surface area " of material is the basic conception in Surface Science, is also the conventional physical quantity in this area, is referred to
It is the size of surface area that the material of unit mass has.This area measure side conventional for material " specific surface area "
Method is based on low temperature nitrogen adsorption-desorption isothermal, then by Brunauer-Emmett-Teller method substance for calculations
Specific surface area（Result is frequently referred to BET specific surface area）；Such Adsorption and desorption isotherms can also obtain the hole contained by solid matter
The information such as size and distribution situation, especially nanoscale Jie view hole road size and the information of distribution.
Part good effect of the invention is as follows：
（1）The preparation process is simple of integral alumina copper-loading catalyst, raw material are cheap, and running cost is low, are suitable for big
Large-scale production.
（2）Preparation technology is environment-friendly, and in addition to using a certain amount of inorganic acid or organic acid, other materials is substantially all
It is nontoxic, non-corrosiveness material；And the inorganic acid and organic acid listed by technical scheme are all more conventional chemical substances, it makes
It is that those skilled in the art know with method, points for attention.
（3）Existing monoblock type ground is utilized with most of（Such as cordierite）Catalytic component is then coated to compare, once into
Type reduces processing step number.
（4）Existing most of integral catalyzer specific surface areas are relatively low（Often it is less than<20 m2/g）, and entirety of the invention
The specific surface area of formula alumina load copper catalyst may be up to 550 m2/g.This is an important advance of the invention.Product is also
With substantial amounts of nanoscale Jie view hole road, size makes it have good catalysis, adsorption applications prospect between 7 ~ 20 nm.
Brief description of the drawings
Fig. 1 integral catalyzer mould schematic diagrames；1 is the part of mould first；2 is the part of mould second；3 is mould
Has the 3rd part；4 is the cylindrical cavity that the part of mould first is included；5 be the part of mould first institute comprising cylindrical cavity 4
Geometrical axis, the axis only to facilitate understand and draw, and non-actual existence；6 is mould the second part crimping section；
7 is mould the second part pressure-bearing part；8 is the compressive plane of mould the second part crimping section；9 is mould the second part pressure-bearing portion
The pressure-bearing surface for dividing；10 is the part crimping section of mould the 3rd；11 is the part pressure-bearing part of mould the 3rd；12 is the part of mould the 3rd
The compressive plane of crimping section；13 is the pressure-bearing surface of the part pressure-bearing part of mould the 3rd；14 representatives are enclosed within the first part and are included
Cylindrical cavity 4 inside molding precursor；8th, 9,12,13 4 directions of arrow are also represented when mould is integrally squeezed by external force
After pressure, the Impact direction of mould is illustrated.
Specific embodiment
Embodiment one,
A kind of high-specific surface area integral alumina copper-loading catalyst, comprising integral alumina copper-loading catalyst preparation side
Method and integral alumina copper-loading catalyst product feature；Wherein preparation method uses the following raw material：
Aluminum precursor：Aluminium hydroxide；
Copper precursors：Copper nitrate；
First additive：The mixture of sesbania powder and guar gum, the two mass ratio is 3 to 1；
Second additive：Carbon black of the granularity less than 60 mesh；
Acid solution：PH value is 0.5 nitric acid and oxalic acid mixed aqueous solution, and wherein the ratio between nitric acid and oxalic acid material mole is 1 ratio
1；
The preparation method of the integral alumina copper-loading catalyst described in the present embodiment, uses integral catalyzer shaping mould
Tool；The mould is as shown in Figure 1 when working；The mould includes the first part of mould 1, the second part of mould 2 and mould
3rd part 3；The part of mould first includes a cylindrical cavity 4；The second part of mould 2 includes mould the second part press section
Divide 6 with mould the second part pressure-bearing part 7；The geometry of the second part of mould crimping section 6 is cylinder, and it has one
Compressive plane 8, the geometry of the compressive plane 8 is circle；Mould the second part pressure-bearing part 7 has a pressure-bearing surface 9；Mould
Three parts 3 include the part crimping section 10 of mould the 3rd and the part pressure-bearing part 11 of mould the 3rd；The part press section of mould the 3rd
The geometry for dividing 10 is cylinder, and it has a compressive plane 12, and the geometry of the compressive plane 12 is circle；Mould the 3rd
Part pressure-bearing part 11 has a pressure-bearing surface 13；The compressive plane 8 of mould the second part crimping section is squeezed with the part of mould the 3rd
The axis direction of the cylindrical cavity that the compressive plane 12 of laminate section can be included from the part of mould first is put into；The part of mould first
Comprising the size of cylindrical cavity 4 be：Cylindrical bottom is the circle of a diameter of 60 mm, a height of 35 mm of cylinder.
The preparation method of the integral alumina carrier described in the present embodiment, by above-mentioned raw materials and integral catalyzer
Mould, its preparation process is comprised the steps of：
Step one, prepare molding precursor；
The assembling of step 2, molding precursor and mould；
Step 3, to molding precursor apply pressure；
Step 4, the roasting of the program of formed blocks.
The specific method of aforementioned four step is as follows：
Step one, prepare molding precursor；Specific method is as follows：
Take aluminum precursor, copper precursors, the first additive, second additive of certain mass；Wherein aluminum precursor quality is 78 g, before copper
The ratio between molal quantity containing aluminium element is 0.025 in molal quantity and aluminum precursor containing copper in body, in conversion cost implementation
Copper precursors（Copper nitrate）Quality be 4.7 g（The crystallization water is not included）；The quality of wherein the first additive is aluminum precursor quality
0.04 times, the quality of the second additive is 0.05 times of aluminum precursor quality；Four kinds of materials uniformly mix, and obtain mixed-powder；And
Acid solution is poured slowly into mixed-powder afterwards, dough is formed, the quality of wherein acid solution is aluminum precursor quality
0.88 times；Hand is first passed through, kneading is carried out to dough using banded extruder afterwards so that aluminum precursor therein, the first addition
Thing, the second additive, acid solution further uniformly mix, and form a moulded pottery not yet put in a kiln to bake for appearance uniform, do not have obvious liquid on moulded pottery not yet put in a kiln to bake
Drop；The moulded pottery not yet put in a kiln to bake referred to as molding precursor obtained by said mixture kneading.
The assembling of step 2, molding precursor and mould；Specific method is as follows：
Molding precursor is filled in the cylindrical cavity 4 that the part of mould first of integral catalyzer mould is included,
As shown in the mark 14 of Fig. 1；The quality of molding precursor is 25.0 g；By the second part of mould crimping section 6 and mould the 3rd 0
The both sides of the cylindrical cavity 4 that part crimping section 10 is included from the part of mould first are respectively charged into；When the part of mould second is squeezed
The cylindrical empty that the compressive plane 8 of laminate section, the compressive plane 12 of the part crimping section of mould the 3rd are included with the part of mould first
The inwall of chamber 4 is collectively forming an airtight cavity, and above-mentioned molding precursor is enclosed in the airtight cavity（As shown at 14）, completion group
Dress step.
Step 3, to molding precursor apply pressure；Specific method is as follows：
The molding precursor that will be assembled is combined with integral catalyzer mould and is placed on a hydraulic press, the part of mould second
The pressure-bearing surface 9 of pressure-bearing part is contacted with the pressure-bearing surface 13 of the part pressure-bearing part of mould the 3rd with the applying press member of hydraulic press,
Allow that hydraulic press pressure applied acts on above-mentioned two pressure-bearing surface；The pressure size of applying is 1.3 MPa；Apply pressure
The power time is 20 min；The molding precursor after being pressurized then is taken out from mould and obtains formed blocks.
Step 4, the roasting of the program of formed blocks；Specific method is as follows：
Operation is dried to formed blocks described in step 3, part volatility moisture is left formed blocks with other materials,
Until the dried quality of formed blocks is about 62% before drying；The present embodiment is using the drying side dried naturally in atmosphere
Method；Formed blocks are placed in a Muffle furnace with temperature programmed control function afterwards carry out heating roasting；The atmosphere of roasting is
Air；Temperature and time relation in program roasting includes three temperature controlling stages, is referred to as the first temperature control stage, second
Temperature control stage and the 3rd temperature control stage；First temperature control stage had an initial temperature, and its value is 50oC, with a termination
Temperature, its value is 500oC；First temperature control stage was 1.5 from initial temperature to final temperature average ramp rateoC/min；
The total time in the first temperature control stage is 5 h；Second temperature control stage had an initial temperature, and its value is 500oC, with one
Final temperature, its value is also 500oC；Second temperature control stage was 0 from initial temperature to final temperature average ramp rateoC/
min；It is 4 h that second temperature controls the total time in stage；3rd temperature control stage had an initial temperature, and its value is 500oC,
With a final temperature, its value is 30oC, the 3rd temperature control stage is from initial temperature to final temperature average ramp rate
For -0.6oC/min；The total time in the 3rd temperature control stage is 13 h.
Complete after step 4, formed blocks are converted into final products integral alumina copper-loading catalyst；Prepared
Journey is completed.
By the sign to above-mentioned final products, the product of above-mentioned preparation method, integral alumina copper-loading catalyst,
Also it is provided simultaneously with following product feature：
（1）The block quality of single integral alumina copper-loading catalyst is up to 6.4 g；
（2）The specific surface area of integral alumina copper-loading catalyst is 203 m2/g；
（3）Copper mass content in single integral alumina copper-loading catalyst block is 3.0 %；
（4）The X-ray diffraction peak of integral alumina copper-loading catalyst only wraps salic SPECTROSCOPIC CHARACTERIZATION, and is free of pass
In the SPECTROSCOPIC CHARACTERIZATION of copper component.
It is above-mentioned（3）（4）2 points combine explanation, and on the basis of with considerable copper component load capacity, copper component is on microcosmic
With decentralization very high.Because seeing in principle, if the microscopic particles of copper component can obtain its X- in 5 more than nm penetrated
Line diffraction maximum.The assay method of the specific surface area of integral alumina copper-loading catalyst is that foregoing low temperature nitrogen is adsorbed-taken off
Attached isothermal collimation method；Tested by same sign, while it has also been found that, integral alumina copper-loading catalyst also has a large amount of nanometers
Level Jie's view hole road.
Embodiment two,
Other are with embodiment one, difference：
Copper precursors：Acetylacetone copper；
Step one, prepare molding precursor；Wherein in copper precursors in molal quantity and aluminum precursor containing copper containing aluminium element mole
The ratio between number is 0.03, and the quality for converting into acetylacetone copper is 11..2 g；
The assembling of step 2, molding precursor and mould；Wherein, the quality of molding precursor is 30.0 g.
Complete after step 4, formed blocks are converted into final products integral alumina copper-loading catalyst；Prepared
Journey is completed.
By the sign to above-mentioned final products, the product of above-mentioned preparation method, integral alumina copper-loading catalyst,
Also it is provided simultaneously with following characteristics：
（1）The block quality of single integral alumina copper-loading catalyst is up to 8.1 g；
（2）The specific surface area of integral alumina copper-loading catalyst is 205 m2/g；
（3）The copper mass content of integral alumina copper-loading catalyst is up to 3.8 %；
（4）The X-ray diffraction peak of integral alumina copper-loading catalyst only wraps salic SPECTROSCOPIC CHARACTERIZATION, and is free of pass
In the SPECTROSCOPIC CHARACTERIZATION of copper component.
Embodiment three,
Other are with embodiment one, difference：
The assembling of step 2, molding precursor and mould；Wherein, the quality of molding precursor is 23.6 g.
Step 4, the roasting of the program of formed blocks；The atmosphere being wherein calcined is purity oxygen；Wherein the first temperature control stage has
One initial temperature, its value is 40oC, with a final temperature, its value is 350oC；First temperature control stage is from initial temperature
It is 2.1 to final temperature average ramp rateoC/min；The total time in the first temperature control stage is 2.5 h；Second temperature control stage
With an initial temperature, its value is 350oC, with a final temperature, its value is 700oC；Second temperature control stage is from starting
Temperature to final temperature average ramp rate be 1oC/min；It is 5.8 h that second temperature controls the total time in stage；3rd temperature
The control stage has an initial temperature, and its value is 700oC, with a final temperature, its value is 30oC, the 3rd temperature control stage
It is -0.55 from initial temperature to final temperature average ramp rateoC/min；The total time in the 3rd temperature control stage is 20.3
h。
Complete after step 4, formed blocks are converted into final products integral alumina copper-loading catalyst；Prepared
Journey is completed.
By the sign to above-mentioned final products, the product of above-mentioned preparation method, integral alumina copper-loading catalyst,
Also it is provided simultaneously with following characteristics：
（1）The block quality of single integral alumina copper-loading catalyst is up to 5.9 g；
（2）The specific surface area of integral alumina copper-loading catalyst is 205 m2/g；
（3）Copper mass content in single integral alumina copper-loading catalyst block is 3.1 %；
（4）The X-ray diffraction peak of integral alumina copper-loading catalyst only wraps salic SPECTROSCOPIC CHARACTERIZATION, and is free of pass
In the SPECTROSCOPIC CHARACTERIZATION of copper component.
Example IV,
Other are with embodiment three, difference：
Copper precursors：Copper chloride；
First additive：Sesbania powder；
Second additive：Ethanol；
Step one, prepare molding precursor；Wherein in copper precursors in molal quantity and aluminum precursor containing copper containing aluminium element mole
The ratio between number is 0.04, converts into copper chloride（Do not calculate the crystallization water）Quality be 5.4 g；
The assembling of step 2, molding precursor and mould；Wherein, the quality of molding precursor is 18.1 g；
Step 3, to molding precursor apply pressure；The pressure size for wherein applying is 1.4 MPa；Applying pressure time is 2 h.
Complete after step 4, formed blocks are converted into final products integral alumina copper-loading catalyst；Prepared
Journey is completed.
By the sign to above-mentioned final products, the product of above-mentioned preparation method, integral alumina copper-loading catalyst,
Also it is provided simultaneously with following characteristics：
（1）The block quality of single integral alumina copper-loading catalyst is up to 4.6 g；
（2）The specific surface area of integral alumina copper-loading catalyst is 221 m2/g；
（3）The copper mass content of integral alumina copper-loading catalyst is up to 4.5 %；
（4）The X-ray diffraction peak of integral alumina copper-loading catalyst only wraps salic SPECTROSCOPIC CHARACTERIZATION, and is free of pass
In the SPECTROSCOPIC CHARACTERIZATION of copper component.
Claims (6)
1. a kind of high-specific surface area integral alumina copper-loading catalyst, prepares comprising integral alumina copper-loading catalyst
Method and integral alumina copper-loading catalyst product feature, it is characterised in that wherein preparation method uses the following raw material：
Aluminum precursor：One kind of aluminium hydroxide, boehmite, or above-mentioned substance arbitrary proportion mixture；
Copper precursors：It is copper nitrate, copper chloride, copper bromide, copper sulphate, copper carbonate, basic copper carbonate, acetylacetone copper, ethylenediamine
One kind in tetraacethyl copper, copper acetate, cupric oxalate, Kocide SD, or above-mentioned substance arbitrary proportion mixture；
First additive：It is sesbania powder, sesbania gum, guar gum, cation guar gum, sodium alginate, carboxymethylcellulose calcium, carboxylic second
One kind in base cellulose, sodium carboxymethylcellulose, sodium hydroxyethlcellulose, galactomannans, or above-mentioned substance is any
The mixture of ratio；
Second additive：Be ethanol, propyl alcohol, butanol, ethylene glycol, propane diols, polyethylene glycol, polyvinyl alcohol, glucose, fructose,
Sucrose, maltose, cellobiose, granularity are less than the carbon black of 60 mesh, granularity less than the one kind in the water soluble starch of 60 mesh,
Or the mixture of above-mentioned substance arbitrary proportion；
Acid solution：A kind of aqueous solution, contains nitric acid, sulfuric acid, hydrochloric acid, acetic acid, oxalic acid, phosphoric acid, citric acid, maleic acid, tartaric acid
In one or more materials, the pH value of the aqueous solution is in the range of 0.0 ~ 4.0；
The preparation method of above-mentioned integral alumina copper-loading catalyst, uses integral catalyzer mould；The shaping mould
Tool includes the part of mould first, the part of mould second and the part of mould the 3rd；The part of mould first includes a cylindrical cavity；
The part of mould second includes mould the second part crimping section and mould the second part pressure-bearing part；Mould the second part press section
The geometry divided is cylinder, and it has a compressive plane, and the geometry of the compressive plane is circle；The part of mould second holds
Laminate section has a pressure-bearing surface；The part of mould the 3rd includes the part crimping section of mould the 3rd and the part pressure-bearing portion of mould the 3rd
Point；The geometry of the part crimping section of mould the 3rd is cylinder, and it has a compressive plane, the geometry of the compressive plane
It is circle；The part pressure-bearing part of mould the 3rd has a pressure-bearing surface；The compressive plane and mould of mould the second part crimping section
The axis direction of the cylindrical cavity that the compressive plane of the 3rd part crimping section can be included from the part of mould first is put into；
The preparation method of above-mentioned integral alumina copper-loading catalyst, by above-mentioned raw materials and integral catalyzer shaping mould
Tool, its preparation process is comprised the steps of：
Step one, prepare molding precursor；
The assembling of step 2, molding precursor and mould；
Step 3, to molding precursor apply pressure；
Step 4, the roasting of the program of formed blocks.
2. high-specific surface area integral alumina copper-loading catalyst according to claim 1, it is characterised in that its preparation
The specific method of the step of method one is as follows：Take aluminum precursor, copper precursors, the first additive, second additive of certain mass；Its
The ratio between molal quantity containing aluminium element is 0.005 ~ 0.15 in molal quantity and aluminum precursor containing copper in middle copper precursors；First addition
The quality of thing is 0.01 ~ 0.1 times of aluminum precursor quality；The quality of the second additive is 0 ~ 0.2 times of aluminum precursor quality；Four kinds
Material uniformly mixes, and obtains mixed-powder；Acid solution is then poured slowly into mixed-powder, dough is formed, wherein
The quality of acid solution is 0.5 ~ 1.3 times of aluminum precursor quality；Kneading is carried out to dough by hand or banded extruder,
So that aluminum precursor therein, the first additive, the second additive, acid solution further uniformly mix, a moulded pottery not yet put in a kiln to bake, moulded pottery not yet put in a kiln to bake are formed
Upper no obvious drop；The moulded pottery not yet put in a kiln to bake referred to as molding precursor obtained by said mixture kneading.
3. high-specific surface area integral alumina copper-loading catalyst according to claim 1, it is characterised in that its preparation
The specific method of the step of method two is as follows：Molding precursor is filled in the part of mould first of integral catalyzer mould
Comprising cylindrical cavity in, the quality of molding precursor is in 2 ~ 400 g ranges；By mould the second part crimping section with
The both sides of the cylindrical cavity that the part crimping section of mould the 3rd is included from the part of mould first are respectively charged into；Molding precursor,
Mould the second part crimping section loads the cylindrical cavity that the part of mould first is included with the part crimping section of mould the 3rd
Order do not limit；Compressive plane, the compressive plane and mould of the part crimping section of mould the 3rd when mould the second part crimping section
The cylindrical empty cavity wall that first part is included is collectively forming an airtight cavity, and it is closed that above-mentioned molding precursor is enclosed in into this
In cavity, number of assembling steps is completed.
4. high-specific surface area integral alumina copper-loading catalyst according to claim 1, it is characterised in that its preparation
The specific method of the step of method three is as follows：The molding precursor that will be assembled is combined with integral catalyzer mould and is placed on one
On platform hydraulic press, the pressure-bearing surface of mould the second part pressure-bearing part, the pressure-bearing surface and hydraulic press of the part pressure-bearing part of mould the 3rd
Applying press member contact so that hydraulic press pressure applied can act on above-mentioned two pressure-bearing surface；The pressure of applying
Size is in the range of 0.1 ~ 5 MPa；Applying pressure time is in the range of 20 s ~ 4 h；Then taken out from mould and received
Molding precursor after pressure obtains formed blocks.
5. high-specific surface area integral alumina copper-loading catalyst according to claim 1, it is characterised in that its preparation
The specific method of the step of method four is as follows：Operation is dried to formed blocks described in step 3, makes part volatility moisture
Formed blocks are left with other materials, until the dried quality of formed blocks is less than 75% before drying；Drying process is included
But be not limited to dry in atmosphere, drying in baking oven or Muffle furnace, dry in vacuum drying chamber, dry in drier, blowing
It is dry, daylight is dried, infrared lamp dry, centrifuge is dried etc. operates, or any combination of aforesaid operations is operated；Afterwards by forming blocks
Body is placed in a heater with temperature programmed control function and is calcined；The atmosphere of roasting is air, or purity oxygen, or arbitrarily
Mixed gas of the oxygenous ratio more than 20%；Temperature and time relation in program roasting includes three temperature controlling stages, point
Have another name called is the first temperature control stage, the second temperature control stage and the 3rd temperature control stage；First temperature control stage had an initial temperature, its
Be worth is 20 ~ 150oCertain value in the range of C, with a final temperature, its value is 300 ~ 750oCertain in the range of C
Value；First temperature control stage is from initial temperature to final temperature average ramp rate 0.5 ~ 8oIn the range of C/min；First
The total time of temperature controlling stages is in the range of 30 min ~ 12 h；Second temperature control stage had an initial temperature, and its value is
300 ~ 750 oCertain value in the range of C, with a final temperature, its value is also 300 ~ 750oCertain in the range of C
Value；Second temperature control stage is from initial temperature to final temperature average ramp rate -2 ~ 2oIn the range of C/min；Second temperature
The total time in control stage is in the range of 1 ~ 6 h；3rd temperature control stage had an initial temperature, and its value is 300 ~ 750oC
In the range of certain value, with a final temperature, its value is 20 ~ 150oCertain value in the range of C；3rd temperature control stage
From initial temperature to final temperature average ramp rate -8 ~ -0.5oIn the range of C/min；3rd temperature control stage it is total when
Between in the range of 2 ~ 24 h；Complete after step 4, formed blocks are converted into final products integral alumina supported copper and urge
Agent；Preparation process is completed.
6. the high-specific surface area integral alumina copper-loading catalyst according to claim 1-5, it is characterised in that its system
The product of Preparation Method, integral alumina copper-loading catalyst is also provided simultaneously with following product feature：Single integral alumina
The block quality of copper-loading catalyst is up to 1 ~ 100 g；The specific surface area of integral alumina copper-loading catalyst be 150 ~
550 m2/g；Copper mass content in single integral alumina copper-loading catalyst block is up to 1 ~ 20 %；It is overall
The X-ray diffraction peak of formula alumina load copper catalyst only wraps salic SPECTROSCOPIC CHARACTERIZATION, and is free of the spectrum on copper component
Learn feature.
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