CN107597178A - A kind of monoblock type molecular sieve type SCR catalyst and preparation method thereof - Google Patents
A kind of monoblock type molecular sieve type SCR catalyst and preparation method thereof Download PDFInfo
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- CN107597178A CN107597178A CN201711075687.5A CN201711075687A CN107597178A CN 107597178 A CN107597178 A CN 107597178A CN 201711075687 A CN201711075687 A CN 201711075687A CN 107597178 A CN107597178 A CN 107597178A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 90
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 39
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 239000011230 binding agent Substances 0.000 claims abstract description 24
- 239000006255 coating slurry Substances 0.000 claims abstract description 12
- 238000000576 coating method Methods 0.000 claims abstract description 10
- 239000011248 coating agent Substances 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 9
- 238000003618 dip coating Methods 0.000 claims abstract description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 239000000919 ceramic Substances 0.000 claims description 26
- 229910052878 cordierite Inorganic materials 0.000 claims description 26
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical group [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 claims description 26
- 239000002002 slurry Substances 0.000 claims description 24
- 239000007787 solid Substances 0.000 claims description 20
- 229910052594 sapphire Inorganic materials 0.000 claims description 19
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- 238000000498 ball milling Methods 0.000 claims description 17
- 230000032683 aging Effects 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 12
- 229910052802 copper Inorganic materials 0.000 claims description 12
- 239000010949 copper Substances 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 235000019260 propionic acid Nutrition 0.000 claims description 3
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 239000011572 manganese Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 229910001428 transition metal ion Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 231100000252 nontoxic Toxicity 0.000 abstract description 2
- 230000003000 nontoxic effect Effects 0.000 abstract description 2
- 230000001603 reducing effect Effects 0.000 abstract description 2
- 241000264877 Hippospongia communis Species 0.000 description 24
- 238000004140 cleaning Methods 0.000 description 12
- 239000000725 suspension Substances 0.000 description 12
- 238000002604 ultrasonography Methods 0.000 description 12
- 238000005406 washing Methods 0.000 description 12
- 238000000227 grinding Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 206010013786 Dry skin Diseases 0.000 description 8
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 241000256844 Apis mellifera Species 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000010422 painting Methods 0.000 description 3
- 229910052573 porcelain Inorganic materials 0.000 description 3
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000000809 air pollutant Substances 0.000 description 1
- 231100001243 air pollutant Toxicity 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004500 asepsis Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
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- 230000001627 detrimental effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
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- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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Abstract
The invention provides a kind of monoblock type molecular sieve type SCR catalyst and preparation method thereof, it is characterised in that：Using molecular sieve catalyst as active component, α Al2O3As binding agent, binding agent is 1 in mass ratio with catalyst:(2 5) coating slurry is configured, using dip-coating method, coating structure is formed in carrier surface, and binding agent and integral catalyzer that catalyst total load quality is 1 10%.Present invention employs simple dip coating process, production process is nontoxic, simple and environmentally-friendly.Load capacity is big and coating number is less, it is possible to reduce production cost.The integral catalyzer prepared by the present invention has higher mechanical strength, and in the presence of ultrasonic field, catalyst quality loss late is less than 20%.And significantly remain the reducing property of molecular sieve catalyst.
Description
Technical field
The present invention relates to a kind of catalysis material field of nitrogen oxides reduction, especially a kind of monoblock type molecular sieve type SCR
Catalyst and preparation method thereof.
Background technology
Nitrogen oxides (the NO of emission of diesel enginex) it is one of main source of air pollutants, it is caused greatly to environment
Destruction.Use ammonia as the Selective Catalytic Reduction of NO of reducing agentx(NH3- SCR) it is the method for alleviating exhaust gas from diesel vehicle pollution
One of.Integral catalyzer with sunken bed pressure drop and high quality transmission efficiency is widely used in NH3-SCR.Integral catalyzer is sudden and violent
Air-impingement is exposed to, thermal shock and chemical attack often lead to the mechanical failure of catalyst.Therefore, it is necessary to prepare with high machinery
The monoblock type SCR catalyst of intensity and catalytic efficiency.
Recently, there is very high hydrothermal stability and NH under oxidative conditions3SAPO-34 (the chabasies of-SCR activity
Structure) catalyst obtain everybody pay close attention to.Losses of the Cu-SAPO-34 to structure and architectural characteristic has much higher hydro-thermal resistance.
This small catalyst not only shows high conversion rate of NOx and N2Selectivity, and high water is also shown at high temperature
Heat endurance.
When preparing high SCR performances integral catalyzer, it is mainly to choose to improve bond strength between coating and carrier vector
One of war.It is reported that can be by adding adhesive such as Al2O3Improve the attachment of ceramic monolith and coating with silica
Power and cohesive force.Such as CN201710209923 patents are disclosed and a kind of prepared with carboxymethyl cellulose or Nano silica sol
Ceramic honeycomb catalyst, this binding agent effectively can load to Multimetal oxide catalyst on ceramic honey comb, but
It is the molecular sieve type catalyst for bigger serface, using traditional γ-Al with high-specific surface area2O3Or silica gel is done
During binding agent, it is possible to form loose coating structure, this is detrimental to the use of integral catalyzer in a practical situation.
In view of this, it is necessory to research and develop a kind of slurry that is simple, being adapted to molecular sieve type integral catalyzer and whole
The preparation method of body formula catalyst.
The content of the invention
It is an object of the invention to a kind of offer monoblock type molecular sieve type SCR is provided to improve the deficiencies in the prior art
Catalyst, it is a further object of the present invention to provide the preparation method of above-mentioned catalyst.
The technical scheme is that：A kind of monoblock type molecular sieve type SCR catalyst, it is characterised in that：Urged with molecular sieve
Agent is as active component, α-Al2O3As binding agent, binding agent is 1 in mass ratio with catalyst:(2-5) configures coating materials
Material, using dip-coating method, coating structure is formed in carrier surface, and binding agent and catalyst total load quality are 1-10%'s
Integral catalyzer.
It is preferred that above-mentioned α-Al2O3Particle diameter be 30-600nm.It is preferred that the carrier is cordierite honeycomb ceramics carrier.
It is preferred that described molecular sieve catalyst is the molecular sieve type catalyst that transition metal ions exchanges to obtain；Wherein molecular sieve is：
ZSM-5, BETA or SAPO-34；Metal ion is：Copper, iron or manganese；And the mass percent of metallic element is 1-10%.
The present invention uses α-Al2O3As binding agent, it is uniformly distributed between the coatings.
Present invention also offers the preparation method of above-mentioned monoblock type molecular sieve type SCR catalyst, it is comprised the following steps that：
(1) after molecular sieve catalyst is ground, 40 mesh sieves are crossed；
(2) binding agent and catalyst are according to being 1 in mass ratio:(2-5) is scattered in deionized water；
(3) pH is adjusted as acidity；
(4) ball milling, slurry is made；
(5) it is (slow) to take out by carrier impregnation in slurry, raffinate is dried up, (at room temperature) aging, dries and then calcines,
Denitrating integral catalyst is made.
The acid that regulation pH is used in preferred steps (3) is the organic acids such as acetic acid or propionic acid；PH scopes are 2-4.
The gross mass solid content of slurry made of preferred steps (4) is 20-30%, and wherein gross mass is catalyst and bonding
Agent quality and.
The rotating speed of ball milling is 300-500r/min in preferred steps (4), and Ball-milling Time is 15-24 hours.
Dip time is 1-10 minutes in preferred steps (5)；Ageing time 1-3 hours；90-120 DEG C of drying temperature, dry
Hour time 1-5；400-900 DEG C of calcining heat, calcination time 2-6 hours.
Beneficial effect：
The invention provides a kind of method and slurry of safe and non-toxic preparation monoblock type molecular sieve type SCR catalyst, adopt
A kind of new binding agent α-Al are taken2O3, the mechanical strength of integral catalyzer can be effectively improved by preparing, and pole
The activity for remaining catalyst of big degree.
Brief description of the drawings
Fig. 1 is embodiment 1-4 Cu-SAPO-34 materials in α-Al2O3As in the case of binding agent different solid contents it is negative
Load rate and mass loss situation map；
Fig. 2 is embodiment 2Cu-SAPO-34 materials with α-Al2O3As not adding additives and the contrast of binding agent and comparative example 1
The Cu-SAPO-34 materials of example 2 are with γ-Al2O3The load factor and mass loss situation map of solid content during as binding agent；
Fig. 3 is figure compared with embodiment 2,3,4,9,10 carries out SCR test results with powder catalyst.
Embodiment
Embodiment 1
Cordierite honeycomb ceramic carrier after roasting is weighed.After the Cu-SAPO-34 catalyst grinding of copper content 5%
40 mesh sieves are crossed, take 16 grams to be dispersed in 4 grams of α-Al2O3In suspension made of (average grain diameter 200nm), 80 grams of water, adjusted with acetic acid
It is 2 to save pH.Ball milling 15 hours under 300r/min, covering for painting solid content 20wt% is made and uses slurry.Carrier cordierite honeycomb is made pottery
Porcelain is dipped in above-mentioned slurry, is slowly withdrawn after 1 minute, dries up raffinate with ear washing bulb, aging 1 hour, 90 DEG C of dryings 1 are small at room temperature
When, then it is warming up to 400 DEG C in Muffle furnace and calcines 2 hours, molecular sieve type monoblock type denitrating catalyst is made, and it is claimed
Weigh to determine coated weight.Carrier is put into water afterwards, dries, is weighed after supersonic cleaning machine ultrasound 30min, to determine
Catalyst quality loses.
Embodiment 2
Cordierite honeycomb ceramic carrier after roasting is weighed.After the Cu-SAPO-34 catalyst grinding of copper content 5%
40 mesh sieves are crossed, take 19.2 grams to be dispersed in 4.8 grams of α-Al2O3In suspension made of (average grain diameter 200nm), 76 grams of water, second is used
Acid for adjusting pH is 4.Ball milling 24 hours under 500r/min, covering for painting solid content 24wt% is made and uses slurry.By carrier cordierite honeybee
Nest ceramics are dipped in above-mentioned slurry, are slowly withdrawn after 10 minutes, dry up raffinate with ear washing bulb, at room temperature aging 3 hours, 120 DEG C
Dry 5 hours, be then warming up to 900 DEG C in Muffle furnace and calcine 6 hours, molecular sieve type monoblock type denitrating catalyst is made, and it is right
It carries out being weighed to determine coated weight.Carrier is put into water afterwards, dries, is claimed after supersonic cleaning machine ultrasound 30min
Weight, to determine that catalyst quality loses.
Embodiment 3
Cordierite honeycomb ceramic carrier after roasting is weighed.After the Cu-SAPO-34 catalyst grinding of copper content 5%
40 mesh sieves are crossed, take 20.8 grams to be dispersed in 5.2 grams of α-Al2O3In suspension made of (average grain diameter 300nm), 74 grams of water, second is used
Acid for adjusting pH is 3.5.Ball milling 20 hours under 400r/min, solid content 26wt% coating slurry is made.By carrier cordierite
Ceramic honey comb is dipped in above-mentioned slurry, is slowly withdrawn after 5 minutes, dries up raffinate with ear washing bulb, at room temperature aging 2 hours, 120 DEG C
Dry 3 hours, then in Muffle furnace with 2 DEG C/min of temperature programmings to 550 DEG C calcine 6 hours, be made molecular sieve type monoblock type take off
Denox catalyst, and it is carried out to be weighed to determine coated weight.Carrier is put into water afterwards, in supersonic cleaning machine ultrasound 30min
After dry, weighed, with determine catalyst quality lose.
Embodiment 4
Cordierite honeycomb ceramic carrier after roasting is weighed.After the Cu-SAPO-34 catalyst grinding of copper content 5%
40 mesh sieves are crossed, take 24 grams to be dispersed in 6 grams of α-Al2O3In suspension made of (average grain diameter 200nm), 70 grams of water, adjusted with propionic acid
It is 3.2 to save pH.Ball milling 22 hours under 400r/min, solid content 30wt% coating slurry is made.By carrier cordierite honeycomb
Ceramics are dipped in above-mentioned slurry, are slowly withdrawn after 5 minutes, dry up raffinate with ear washing bulb, at room temperature aging 2 hours, 110 DEG C of dryings
4 hours, then in Muffle furnace with 2 DEG C/min of temperature programmings to 550 DEG C calcine 4 hours, be made molecular sieve type monoblock type denitration urge
Agent, and it is carried out to be weighed to determine coated weight.Carrier is put into water afterwards, dried after supersonic cleaning machine ultrasound 30min
It is dry, weighed, to determine that catalyst quality loses.
Embodiment 1-4 Cu-SAPO-34 materials are in α-Al2O3As the load factor of different solid contents in the case of binding agent and
Mass loss situation map as shown in Figure 1 (left side is load factor, and the right is mass loss), illustrates the total solid content 20- of slurry
30wt% is more suitable coated conditions.
Embodiment 5
Cordierite honeycomb ceramic carrier after roasting is weighed.By mistake after the Cu-ZSM-5 catalyst grinding of copper content 5%
40 mesh sieves, 16 grams are taken to be dispersed in 4 grams of α-Al2O3In suspension made of (average grain diameter 200nm), 80 grams of water, adjusted with acetic acid
PH is 3.Ball milling 20 hours under 400r/min, solid content 20wt% coating slurry is made.By carrier cordierite honeycomb ceramic
It is dipped in above-mentioned slurry, is slowly withdrawn after 3 minutes, dries up raffinate with ear washing bulb, aging 2 hours, 110 DEG C of dryings 4 are small at room temperature
When, then calcined 4 hours to 550 DEG C with 2 DEG C/min of temperature programmings in Muffle furnace, molecular sieve type monoblock type denitration catalyst is made
Agent, and it is carried out to be weighed to determine coated weight.Carrier is put into water afterwards, dried after supersonic cleaning machine ultrasound 30min,
Weighed, to determine that catalyst quality loses.
Embodiment 6
Cordierite honeycomb ceramic carrier after roasting is weighed.40 will be crossed after the Cu-BETA catalyst grinding of copper content 5%
Mesh sieve, 16 grams are taken to be dispersed in 4 grams of α-Al2O3In suspension made of (average grain diameter 200nm), 80 grams of water, with second acid for adjusting pH
For 3.Ball milling 20 hours under 400r/min, solid content 20wt% coating slurry is made.Carrier cordierite honeycomb ceramic is soaked
In above-mentioned slurry, it is slowly withdrawn after 3 minutes, raffinate is dried up with ear washing bulb, aging 2 hours at room temperature, 110 DEG C of dryings 4 hours,
Then calcined 4 hours to 550 DEG C with 2 DEG C/min of temperature programmings in Muffle furnace, molecular sieve type monoblock type denitrating catalyst be made,
And it is carried out to be weighed to determine coated weight.Carrier is put into water afterwards, dries, enters after supersonic cleaning machine ultrasound 30min
Row is weighed, to determine that catalyst quality loses.
Embodiment 7
Cordierite honeycomb ceramic carrier after roasting is weighed.After the Mn-SAPO-34 catalyst grinding of copper content 5%
40 mesh sieves are crossed, take 13.3 grams to be dispersed in 6.6 grams of α-Al2O3In suspension made of (average grain diameter 200nm), 80 grams of water, second is used
Acid for adjusting pH is 3.Ball milling 20 hours under 400r/min, solid content 20wt% coating slurry is made.By carrier cordierite honeybee
Nest ceramics are dipped in above-mentioned slurry, are slowly withdrawn after 3 minutes, dry up raffinate with ear washing bulb, at room temperature aging 2 hours, and 110 DEG C dry
Dry 4 hours, then calcined 4 hours to 550 DEG C with 2 DEG C/min of temperature programmings in Muffle furnace, molecular sieve type monoblock type denitration is made
Catalyst, and it is carried out to be weighed to determine coated weight.Carrier is put into water afterwards, after supersonic cleaning machine ultrasound 30min
Drying, is weighed, to determine that catalyst quality loses.
Embodiment 8
Cordierite honeycomb ceramic carrier after roasting is weighed.After the Fe-SAPO-34 catalyst grinding of copper content 5%
40 mesh sieves are crossed, take 16.7 grams to be dispersed in 3.3 grams of α-Al2O3In suspension made of (average grain diameter 80nm), 80 grams of water, second is used
Acid for adjusting pH is 3.Ball milling 20 hours under 400r/min, solid content 20wt% coating slurry is made.By carrier cordierite honeybee
Nest ceramics are dipped in above-mentioned slurry, are slowly withdrawn after 3 minutes, dry up raffinate with ear washing bulb, at room temperature aging 2 hours, and 110 DEG C dry
Dry 4 hours, then calcined 4 hours to 550 DEG C with 2 DEG C/min of temperature programmings in Muffle furnace, molecular sieve type monoblock type denitration is made
Catalyst, and it is carried out to be weighed to determine coated weight.Carrier is put into water afterwards, after supersonic cleaning machine ultrasound 30min
Drying, is weighed, to determine that catalyst quality loses.
Embodiment 9
Cordierite honeycomb ceramic carrier after roasting is weighed.After the Cu-SAPO-34 catalyst grinding of copper content 1%
40 mesh sieves are crossed, take 16 grams to be dispersed in 4 grams of α-Al2O3In suspension made of (average grain diameter 200nm), 80 grams of water, adjusted with acetic acid
It is 3 to save pH.Ball milling 20 hours under 400r/min, solid content 20wt% coating slurry is made.Carrier cordierite honeycomb is made pottery
Porcelain is dipped in above-mentioned slurry, is slowly withdrawn after 3 minutes, dries up raffinate with ear washing bulb, at room temperature aging 2 hours, 110 DEG C of dryings 4
Hour, then in Muffle furnace with 2 DEG C/min of temperature programmings to 550 DEG C calcine 4 hours, be made molecular sieve type monoblock type denitration urge
Agent, and it is carried out to be weighed to determine coated weight.Carrier is put into water afterwards, dried after supersonic cleaning machine ultrasound 30min
It is dry, weighed, to determine that catalyst quality loses.
Embodiment 10
Cordierite honeycomb ceramic carrier after roasting is weighed.After the Cu-SAPO-34 catalyst grinding of copper content 10%
40 mesh sieves are crossed, take 16 grams to be dispersed in 4 grams of α-Al2O3In suspension made of (average grain diameter 500nm), 80 grams of water, adjusted with acetic acid
It is 3 to save pH.Ball milling 20 hours under 400r/min, solid content 20wt% coating slurry is made.Carrier cordierite honeycomb is made pottery
Porcelain is dipped in above-mentioned slurry, is slowly withdrawn after 3 minutes, dries up raffinate with ear washing bulb, at room temperature aging 2 hours, 110 DEG C of dryings 4
Hour, then in Muffle furnace with 2 DEG C/min of temperature programmings to 550 DEG C calcine 4 hours, be made molecular sieve type monoblock type denitration urge
Agent, and it is carried out to be weighed to determine coated weight.Carrier is put into water afterwards, dried after supersonic cleaning machine ultrasound 30min
It is dry, weighed, to determine that catalyst quality loses.
The catalyst loadings of each embodiment and mass loss are as shown in table I
Table I：Catalyst loadings and mass loss
| Catalyst | Load capacity (wt%) | Mass loss (wt%) |
| Embodiment 1 | 3.67 | 8.24 |
| Embodiment 2 | 4.08 | 9.62 |
| Embodiment 3 | 7.11 | 10.85 |
| Embodiment 4 | 7.32 | 11.73 |
| Embodiment 5 | 4.28 | 7.35 |
| Embodiment 6 | 4.38 | 12.21 |
| Embodiment 7 | 4.21 | 8.39 |
| Embodiment 8 | 4.33 | 9.53 |
| Embodiment 9 | 4.01 | 8.34 |
| Embodiment 10 | 3.85 | 7.35 |
Comparative example 1
Cordierite honeycomb ceramic carrier after roasting is weighed.40 mesh sieves are crossed after Cu-SAPO-34 catalyst is ground, are taken
20 grams are dispersed in 80 grams of water in manufactured suspension, and regulation pH is 3.Ball milling 20 hours, are made solid content under 400r/min
20wt% coating slurry.Carrier cordierite honeycomb ceramic is dipped in above-mentioned slurry, is slowly withdrawn after 3 minutes, with washing ear
Ball dries up raffinate, aging 2 hours at room temperature, 110 DEG C of dryings 4 hours, then in Muffle furnace with 2 DEG C/min of temperature programmings to 550
DEG C calcining 4 hours, is made molecular sieve type monoblock type denitrating catalyst, and it is carried out to be weighed to determine coated weight.It will carry afterwards
Body is put into water, is dried, is weighed after supersonic cleaning machine ultrasound 30min, to determine that catalyst quality loses.
Comparative example 2
Cordierite honeycomb ceramic carrier after roasting is weighed.40 mesh sieves are crossed after Cu-SAPO-34 catalyst is ground, are taken
16 grams are dispersed in 4 grams of γ-Al2O3, be 3 with second acid for adjusting pH in 80 grams of suspensions made of water.Ball milling 20 is small under 400r/min
When, solid content 20wt% coating slurry is made.Carrier cordierite honeycomb ceramic is dipped in above-mentioned slurry, delayed after 3 minutes
It is slow to take out, raffinate is dried up with ear washing bulb, at room temperature aging 2 hours, 110 DEG C of dryings 4 hours, then in Muffle furnace with 2 DEG C/min
Temperature programming is calcined 4 hours to 550 DEG C, molecular sieve type monoblock type denitrating catalyst is made, and it is carried out to be weighed to determine painting
The amount of covering.Carrier is put into water afterwards, dries, is weighed after supersonic cleaning machine ultrasound 30min, to determine catalyst quality
Loss.
Embodiment 2Cu-SAPO-34 materials are with α-Al2O3As binding agent and comparative example 1 not adding additives and comparative example 2
Cu-SAPO-34 materials are with γ-Al2O3The load factor and mass loss situation map of solid content during as binding agent are as shown in Figure 2；
As a result α-Al are shown2O3It is more suitable for molecular sieve type catalyst load.
In order to verify beneficial effects of the present invention, NOx SCR catalytic test has been carried out with 8 cm diameters and 50
The fixed bed quartz tube reactor of centimetre length carries out SCR tests.By in the addition reactor catalysis layer prepared, it is heated to
550 DEG C (referring to reaction conditions in " Table II ") and kept for 1 hour in a nitrogen atmosphere.And compared with powder catalyst
Compared with reaction result is as shown in Figure 3.It can be seen that in 250-350 DEG C of temperature range, the obtained denitrating integral catalyst pair of the present invention
NOx removal efficiency (other embodiment to NOx removal efficiency also more than 90%) more than 90%, and significantly retain
The catalytic performance of powder catalyst.
Table II：SCR test conditions
In summary, the invention provides a kind of binding agent for being more suitable for molecular sieve type monoblock type denitrating catalyst, and
And the preparation method of its slurry is provided, preparation process asepsis environment-protecting.And using α-Al2O3It can be obtained more as binding agent
High catalyst bond strength.And provide a kind of preparation side for being suitable for molecular sieve type catalyst and preparing integral catalyzer
Method, the reducing property of powder catalyst can be effectively kept by this preparation method.And this preparation method can be with
The load factor of catalyst is adjusted by changing solid content, coating number can be effectively reduced, saves production cost, is adapted to more
Large-scale production.
Claims (9)
- A kind of 1. monoblock type molecular sieve type SCR catalyst, it is characterised in that：Using molecular sieve catalyst as active component, α- Al2O3As binding agent, binding agent is 1 in mass ratio with catalyst:(2-5) configures coating slurry, using dip-coating method, Carrier surface forms coating structure, and integral catalyzer of the binding agent with catalyst total load quality for 1-10%.
- 2. catalyst according to claim 1, it is characterised in that：Described α-Al2O3Particle diameter be 30-600nm.
- 3. catalyst according to claim 1, it is characterised in that：The carrier is cordierite honeycomb ceramics carrier.
- 4. catalyst according to claim 1, it is characterised in that：Described molecular sieve catalyst is handed over for transition metal ions The molecular sieve type catalyst got in return；Wherein molecular sieve is：ZSM-5, BETA or SAPO-34；Metal ion is：Copper, iron or manganese； And the mass percent of metallic element is 1-10%.
- 5. a kind of method for preparing monoblock type molecular sieve type SCR catalyst as claimed in claim 1, it is comprised the following steps that：(1) after molecular sieve catalyst is ground, 40 mesh sieves are crossed；(2) binding agent and catalyst are according to being 1 in mass ratio:(2-5) is scattered in deionized water；(3) pH is adjusted as acidity；(4) ball milling, slurry is made；(5) by carrier impregnation in slurry, take out, dry up raffinate, aging, dry and then calcine, denitrating integral catalysis is made Agent.
- 6. according to the method for claim 5, it is characterised in that：The acid that regulation pH is used in step (3) is acetic acid or propionic acid； PH scopes are 2-4.
- 7. according to the method for claim 5, it is characterised in that：The gross mass solid content of slurry made of step (4) is 20- 30%, wherein gross mass be catalyst and binding agent quality and.
- 8. according to the method for claim 5, it is characterised in that：The rotating speed of ball milling is 300-500r/min in step (4), ball Consume time as 15-24 hours.
- 9. according to the method for claim 5, it is characterised in that：Dip time is 1-10 minutes in step (5)；Ageing time 1-3 hours；90-120 DEG C of drying temperature, hour drying time 1-5；400-900 DEG C of calcining heat, calcination time 2-6 hours.
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| CN115178292A (en) * | 2022-06-29 | 2022-10-14 | 凯龙蓝烽新材料科技有限公司 | High-sulfur-resistance molecular sieve-based monolithic SCR catalyst and preparation method thereof |
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