CN105642369B - A kind of reduction NOxThe alumina support forming processing method of discharge - Google Patents
A kind of reduction NOxThe alumina support forming processing method of discharge Download PDFInfo
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- CN105642369B CN105642369B CN201410723785.5A CN201410723785A CN105642369B CN 105642369 B CN105642369 B CN 105642369B CN 201410723785 A CN201410723785 A CN 201410723785A CN 105642369 B CN105642369 B CN 105642369B
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Abstract
The present invention discloses a kind of alumina support forming processing method, including following content: (1) prepare adhesive or peptizing agent containing nitric acid, by alumina powder with containing nitric acid adhesive or peptizing agent mix, then carry out kneading, roll, form, drying；(2) preparation ammonium class is inorganic or solution of organic compound, the carrier of spray impregnation steps (1) are then dried；(3) carrier prepared by step (3) is roasted, the roasting is divided to two sections of progress, and first segment seals 1 ~ 3h of roasting at 200 ~ 350 DEG C, and second segment normal pressure at 450 ~ 600 DEG C roasts 1 ~ 3h.This method can reduce the discharge of NOx.
Description
Technical field
The present invention relates to a kind of alumina support forming processing methods for reducing NOx emission.
Background technique
As crude quality becomes weight, variation year by year, environmental regulation is increasingly stringent, and market is continuous to the demand of clear gusoline
Increase, so that the hydrogen addition technology of production clean fuel is more and more widely used.Distillate hydrogenation processing refers to high temperature height
Hydrodesulfurization, hydrodenitrogeneration, hydrogenation deoxidation, hydrodemetallization and not occur on catalyst surface for pressure, feedstock oil and hydrogen
Saturated hydrocarbons adds the catalysis reaction such as hydrogen saturation.Since crude quality is deteriorated and refinery is to increase economic efficiency year by year, start universal
Using crude oil deep vacuum distillation technology, so that doing for vacuum distillate has been increased to 600 DEG C or more by original 520 DEG C, it is close
Spend that increasing, boiling range is higher and higher, the molecular weight of contained hydrocarbon molecule is increasing, impurity content is also more and more, especially
The complicated condensed-nuclei aromatics compounds content of sulfur-bearing, nitrogen impurity greatly increases, and the abjection difficulty of impurity greatly increases, and is easy
Carbon deposit coking is caused to reduce catalyst activity.Therefore, hydrotreated feed oil and product all to hydrotreating techniques and add hydrogen
Handling catalyst, more stringent requirements are proposed.
The geometric shape and geometric dimension of catalyst, to fluid resistance, air velocity, bed temperature gradient distribution, concentration
Gradient distribution etc. all has a major impact.In order to give full play to the catalytic performance of catalyst, optimal shape and size should be selected,
This just needs to select most suitable forming method.Shaping of catalyst technology mainly include spray shaping, forming oil column, extrusion at
Type, compression molding and rotational forming etc..The fixed bed carried type hydrotreating catalyst of oil refining field of hydrogenation generallys use extrusion
Forming method.Need to be added a certain amount of adhesive or diluted acid peptizing agent during extruded moulding, effect is to play bonding to make
With guarantee molding rear catalyst has certain geometry appearance shape and higher pressure resistance, wear-resistant strength.The preparation master of adhesive
If uniformly being mixed according to a certain percentage by diluted acid with oxide dry glue, agitated, ageing obtains jelly.
During catalyst or carrier extruded moulding, adhesive generallys use acid stronger non-volatile inorganic acid and hole
Hold the mixing jelly of lesser oxide.If CN93117528.3 is using the nothing of aluminium oxide, titanium oxide, silica and clay
Machine oxide or inorganic matter oxide mixture and inorganic acid prepare adhesive.US8,021,540 uses inorganic matter powdery group
It is allocated as shaping of catalyst adhesive, such as clay, montmorillonite, waterglass, and US7,687,676 then be used directly inorganic acid acid
The silica solution or Aluminum sol of change are as the adhesive during shaping of catalyst.The effect of adhesive is by catalyst or carrier
After evenly mixing, peptization becomes the paste shape that can be squeezed to various components, and (banded extruder) carries out extruded moulding at elevated pressures, then
It is dried and calcination process.In dry and roasting process, in strong acid and small orifice oxide between the contact interface of each component
Under the action of chemically react, staggeredly connected chemical bond is formed each other, so that catalyst or carrier have one
Fixed geometric shape and very high pressure resistance, wear-resistant strength.Wherein the effect of small orifice oxide is not easy in catalyst or carrier
The hole of interaction holds between biggish component, plays the role of connection or grafting, it is made to combine closely each other, improve at
The mechanical strength of type rear catalyst or carrier.Therefore, the acids needs used as catalyst or carrier forming adhesive have
Stronger acidity, and the noresidue impurity after being thermally decomposed；The aperture that uses hold oxide then need to have lesser granularity and
Pore volume.
Nitric acid has many advantages, such as that acid strong, easy decomposition, price are low, and noresidue in the catalyst after decomposition, is to prepare
The most-often used inorganic acid of hydrogenation catalyst, and industrially caking property is generallyd use using small orifice oxide in most adhesives
Energy is good, prepares easy γ-aperture aluminum oxide precursor object.CN97121663.0 give a kind of beta-zeolite molecular sieve catalyst and
Preparation method is prepared in the preparation process of catalyst using the aluminum oxide precursor object (boehmite) that nitric acid and aperture hold
Adhesive, obtain preferable effect.However nitric acid will be released a large amount of NO in subsequent roasting process by thermal decompositionx, make
At comparable environmental hazard, NOxThe pollutant type for being difficult purified treatment, become restrict catalyst production link it is important because
One of element.NOxIt is a kind of main atmospheric pollutant, forms acid rain, photochemical fog and cause ozone hole
One of primary pollution source.In addition, a large amount of NOxGeneration also can cause heavy corrosion to production equipment and operator's health is made
At very big damage.According to statistics, 1 ton of hydrogenation catalyst of every production will generate about 45 standard cubic meter NOx, these NOx are with lower dense
Degree is dispersed in catalyst production tail gas, forms volume largely difficult emission.With hydrogen addition technology flourish,
The usage amount of hydrogenation catalyst is also rapidly increasing, this also causes the pollution problem of NOx and day to aggravate, and the solution of this problem is
It is imperative.
It is increasingly stringent with environmental law, solve the NO in catalyst preparation processxPollution problem increasingly receives pass
Note.For cleaning for catalyst production process, people have selected some cleaning nitrogenfree oxides in catalyst preparation process
The raw material of discharge.Therefore, the substitution acids of nitric acid is selected to the project that attracts attention during shaping of catalyst.
CN00110016.5 and CN00123221.5 describes two kinds of oil refining class loaded catalyst extruded moulding methods respectively.In acidity
In the selection of peptizing agent, in addition to nitric acid can be used as Aci-Jel solvent, two schemes have been all made of more inorganic and have had
The selection of machine acids, if inorganic acid can choose the combination of phosphoric acid, hydrochloric acid, sulfuric acid or several acid, organic acid can be with formic acid, second
Acid, oxalic acid, citric acid etc..However in addition to nitric acid, most of inorganic acids, such as sulfuric acid, hydrochloric acid, hydrofluoric acid thermally decomposed after
There is impurity residue problems, are post-processed, and the peptizing agent (or peptization acid) directly as shaping of catalyst is not suitable for.
For organic acid, noresidue element after majority is thermally decomposed, but the wherein relatively low acetic acid of price, citric acid and acetic acid
Deng, acid on the weak side, peptization performance is not strong, be not suitable for the peptizing agent separately as shaping of catalyst, thus nitric acid as plus hydrogen urge
The most common sour peptizing agent of agent, is widely applied in the industrial production for a long time.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of alumina support forming processing method for reducing NOx emission.
Alumina support forming processing method of the present invention includes following content:
(1) prepare adhesive or peptizing agent containing nitric acid, by alumina powder with containing nitric acid adhesive or peptizing agent mix,
Then kneading is carried out, rolls, form, drying；
(2) preparation ammonium class is inorganic or place is then dried in solution of organic compound, the carrier of spray impregnation steps (1)
Reason, ammonium class is inorganic or solution of organic compound in ammonium class is inorganic or the mass concentration of organic compound is 1.0~15.0gNH4 +/
100mL, it is based on 5:1~1:5 that spray flow, which consolidates volume ratio by liquid,；
(3) carrier prepared by step (3) is roasted, the roasting is divided to two sections of progress, and first segment is at 200 ~ 350 DEG C
Sealing 1 ~ 3h of roasting, second segment normal pressure at 450 ~ 600 DEG C roast 1 ~ 3h.
The method of the present invention takes the aperture boehmite, aperture silica gel, aperture magnesium hydroxide, aperture of metering in step (1)
One or more of contained amorphous silica-alumina dry glue is sufficiently mixed with dust technology, prepares the acid adhesive that butt is 10 ~ 40%,
The molar ratio of total acid and small porous aluminum oxide is 0.05~3.0, preferably 0.05~1.8 in acid adhesive, and aperture intends thin water aluminium
Stone, aperture silica gel, aperture magnesium hydroxide or aperture contained amorphous silica-alumina dry glue granularity require less than 100 mesh, preferably smaller than 180
Mesh；Concentration of nitric acid is 1.0 ~ 20.0g/100mL in nitric acid peptizing agent.
The method of the present invention, step (1) carrier after molding are bar shaped, cylindric, clover, bunge bedstraw herb, tooth ball or other
Irregular strip.
Other support materials appropriate can be added in step (1) in the method for the present invention as needed, as aluminium oxide, silica,
One or more of magnesia, titanium oxide, zirconium oxide, amorphous silica-alumina, molecular sieve, active carbon, can also add plus hydrogen is living
Property component or auxiliary agent, active component are generally the one or more of group vib and VIII metal, such as W, Mo, Ni and Co, wherein VIB
For ammonium salt or acidic oxide, VIII metal uses the form of nitrate, one or more of auxiliary agent such as P, F, B, Zr, Ti
Compound.Support material can be the precursor of above-mentioned carrier component itself or carrier component, carrier material and support material
Selection be those skilled in the art Conventional wisdom.
The method of the present invention, ammonium class inorganic compound can be ammonium carbonate, urea, ammonium sulfate, ammonium chloride, sulphur in step (2)
Change the mixing of one or more of ammonium；Ammonium class organic compound can be ammonium formate, ammonium acetate, ethanedioic acid ammonium, in ammonium benzoate
One or more of mixing.Preferred ammonium carbonate, urea and ammonium acetate in all ammonium class inorganic compounds or organic compound.
The method of the present invention, step (2) drying process use microwave drying, and microwave power is 10~500 watts/gram object to be processed
Material, the processing time, drying temperature was 60~180 DEG C, every gram of object to be processed at 0.5~3 hour, 100~2000MHz of microwave frequency
The power and the product of time for expecting microwave treatment are not less than 5 watts of hours, preferably not less than 15 watts of hours.Low-temperature microwave dries energy
Enough promote that ammonium class is inorganic or organic compound carry it is intracorporal be uniformly distributed, reduce the discharge of NOx emission.
In the method for the present invention, first segment sealing roasting carries out under an inert atmosphere in step (3), preferably in carbon dioxide gas
It is carried out under atmosphere, second segment roasting carries out in air atmosphere.It is roasted under carbon dioxide atmosphere, turning for nitrogen dioxide can be promoted
Change.
A kind of carrier prepared using the above method, 1.0~6.0mm of diameter, preferably 1.2~3.0mm, crushing strength 140 ~
280N/cm, preferably 160 ~ 240N/cm；Abrasion resistance 0 ~ 2%；240 ~ 600m of specific surface area2/ g, preferably 300 ~ 480m2/g；Kong Rong
0.30 ~ 1.00cm of product3/ g, preferably 0.40 ~ 0.80cm3/g；0.40 ~ 0.80g/cm of bulk density3, preferably 0.50 ~ 0.70g/cm3。
The present invention is directed to the NOx pollution problem of carrier forming process, introduces ammonium-containing compound in carrier last handling process,
In subsequent roasting process, ammonium compounds under a certain pressure and at a temperature of can release NOx with nitrate anion decomposition and react
Nitrogen and water are generated, to reduce or eliminate the conventional use of nitric acid acid peptizing agent of forming process or adhesive decomposes release
NOx realizes cleaning for hydrogenation catalyst molding process.The calcination process process of catalyst or carrier of the invention point
It is two sections, the NOx for enabling nitric acid to decompose is synchronous with the ammonia that ammonium-containing compound decomposes to carry out adequately in the duct of carrier
Reaction reduces or avoids the discharge of NOx while guaranteeing carrier property, realizes clean manufacturing.
Specific embodiment
The effect and effect of the method for the present invention are illustrated below with reference to embodiment, but following embodiment is not constituted to this
The limitation of inventive method.
Example 1
1280mL dilute nitric acid solution (concentration is 4g nitric acid/100mL) is taken, 720g aperture boehmite (moral is gradually added into
State produces SB powder), after static 20min, stir evenly, at white translucent paste shape, static ageing 8h, is prepared viscous at room temperature
Mixture.Taking 580g macroporous aluminium oxide, (Noya Inc.'s production is cut in Tianjin, and hole holds 0.80mL/g, specific surface area 295m2/ g, butt
72.1%) 6g sesbania powder, is added, and 562.9g adhesive is added, rolls 30 minutes, suitable distilled water is added, make mixture at
Paste shape, extrusion can be squeezed, banded extruder hole board diameter is 1.5mm clover.Dry 2h at 120 DEG C after molding.Then in carrier
It is 14.4g urea/100mL aqueous solution of urea that 320mL concentration is uniformly sprayed in dried strip, is then dried and two sections roast
It burns, dry to use microwave drying, drying temperature is 100 DEG C, and microwave power handles the time at 90 minutes in 10 watts/gram, Microwave Frequency
Rate 915MHz.320 DEG C of maturing temperature are sealed under first segment air atmosphere, constant temperature 1.5h；Second segment pressure is normal pressure, air gas
Atmosphere, 550 DEG C of maturing temperature, constant temperature time 3h, preparing catalyst number is HT-1S.
Embodiment 2
In 1 preparation process of example, first segment roasting is used into CO2Gas heats up after being replaced, and sealing roasting is in CO2
It is carried out under atmosphere, for remaining step with embodiment 1, preparing catalyst number is HT-2S.
Embodiment 3
In 1 preparation process of example, microwave drying is not used after impregnating urea, 4 hours dry at 120 DEG C, remaining step
Suddenly with embodiment 1, preparing catalyst number is HT-3S.
Example 4
Adhesive in example 1 is changed to the dilute nitric acid solution 280mL of 4.0g/100mL, carrier strip sprays 360mL after drying
Concentration is 12.6g ammonium carbonate/100mL sal volatile, and first segment seals roasting 3h at 250 DEG C, and second segment is at 500 DEG C
Normal pressure roasts 2h, and other same examples 1, preparing bearer number is HT-4S.
Comparative example 1
Urea in example 1 is added during kneading and compacting, for additional amount with embodiment 1, other preparation steps are same
Example 1 prepares carrier, number CB-1S.
Comparative example 2
After having impregnated urea in example 1, catalyst dried strip carries out one section of conventional roasting, open roasting, roasting
Condition is 550 DEG C, time 6h, and other same examples 1 prepare catalyst, number CB-2S.
The aluminium oxide catalyst (or carrier) of the embodiment of the present invention and comparative example preparation, physico-chemical property are listed in table 1.
The physico-chemical property of 1. carrier of table or catalyst
| Number | HT-1S | HT-2S | HT-3S | HT-4S | CB-1S | CB-2S |
| Heap ratio, g/mL | 0.602 | 0.589 | 0.599 | 0.572 | 0.608 | 0.572 |
| Crushing strength, N/cm | 169 | 183 | 187 | 199 | 89 | 184 |
| Abrasion resistance, wt% | 0.9 | 0.4 | 0.4 | 0.7 | 3.2 | 0.8 |
| SBET, m2/g | 344 | 355 | 347 | 362 | 312 | 324 |
| VSIN, mL/g | 0.628 | 0.640 | 0.631 | 0.624 | 0.424 | 0.612 |
| RBET *1, nm | 8.0 | 8.2 | 8.8 | 8.8 | 4.6 | 7.4 |
| Drying process tail gas NOx content*2, ppm | 11 | 5 | 6 | 5 | 15 | 110 |
| It roasts to 260 DEG C of tail gas NOx contents, ppm | 28 | 5 | 10 | 27 | 10 | 3070 |
| It roasts to 320 DEG C of tail gas NOx contents, ppm | 24 | 0 | 0 | 12 | 20 | 1200 |
* 1:RBETFor the average pore diameter of BET method measurement.
* the method characterization that 2:NOx content is absorbed using lye.
Claims (14)
1. a kind of alumina support forming processing method, it is characterised in that: including following content:
(1) prepare adhesive or peptizing agent containing nitric acid, by alumina powder with containing nitric acid adhesive or peptizing agent mix, then
Kneading is carried out, rolls, form, drying；
(2) preparation ammonium class is inorganic or solution of organic compound, the carrier of spray impregnation steps (1) are then dried, ammonium
Class is inorganic or solution of organic compound in ammonium class is inorganic or the mass-volume concentration of organic compound is 1.0~15.0gNH4 +/
100mL, it is based on 5:1~1:5 that spray flow, which consolidates volume ratio by liquid,；
(3) carrier prepared by step (2) is roasted, the roasting is divided to two sections of progress, and first segment is in 200 ~ 350 DEG C, dioxy
Change 1 ~ 3h of sealing roasting under carbon atmosphere, second segment normal pressure under 450 ~ 600 DEG C, air atmosphere roasts 1 ~ 3h；
Wherein, ammonium class inorganic compound described in step (2) is one of ammonium carbonate, ammonium sulfate, ammonium chloride, ammonium sulfide or several
Kind mixing；Ammonium class organic compound described in step (2) is urea, in ammonium formate, ammonium acetate, ethanedioic acid ammonium, ammonium benzoate
One or more mixing.
2. according to the method described in claim 1, it is characterized by: taking aperture boehmite, the aperture of metering in step (1)
One or more of silica gel, aperture magnesium hydroxide, aperture contained amorphous silica-alumina dry glue are sufficiently mixed with dust technology, prepare butt
For 10 ~ 40% acid adhesive.
3. according to the method described in claim 2, it is characterized by: in acid adhesive total acid and small porous aluminum oxide molar ratio
It is 0.05~3.0, the granularity of aperture boehmite, aperture silica gel, aperture magnesium hydroxide or aperture contained amorphous silica-alumina dry glue
It is required that less than 100 mesh.
4. according to the method described in claim 3, it is characterized by: in acid adhesive total acid and small porous aluminum oxide molar ratio
It is 0.05~1.8, the granularity of aperture boehmite, aperture silica gel, aperture magnesium hydroxide or aperture contained amorphous silica-alumina dry glue
It is required that less than 180 mesh.
5. according to the method described in claim 1, it is characterized by: concentration of nitric acid is 1.0 ~ 20.0g/ in nitric acid peptizing agent
100mL。
6. according to the method described in claim 1, it is characterized by: step (1) carrier after molding be bar shaped, it is cylindric, three
Leaf grass, bunge bedstraw herb or tooth ball.
7. according to the method described in claim 1, it is characterized by: in step (1) kneading process be added aluminium oxide, silica,
One or more of magnesia, titanium oxide, zirconium oxide, amorphous silica-alumina, molecular sieve, active carbon.
8. according to the method described in claim 1, it is characterized by: in step (1) kneading process add hydrogenation active component or
Auxiliary agent, active component are one or more of group vib and VIII metal.
9. according to the method described in claim 8, it is characterized by: active component is one or more of W, Mo, Ni, Co.
10. according to the method described in claim 1, it is characterized by: ammonium class inorganic compound is ammonium carbonate, ammonium class organic compound
Object is ammonium acetate or urea.
11. according to the method described in claim 1, it is characterized by: step (2) drying process uses microwave drying, microwave function
Rate is 10~500 watt/gram treating materials, the processing time at 0.5~3 hour, 100~2000MHz of microwave frequency, drying temperature
It is 60~180 DEG C, the power and the product of time of every gram for the treatment of material microwave treatment are not less than 5 watts of hours.
12. according to the method for claim 11, it is characterised in that: the power of every gram for the treatment of material microwave treatment and time
Product be not less than 15 watts of hours.
13. a kind of carrier prepared using one of claim 1-12 method, it is characterised in that: 1.0~6.0mm of Carrier diameters,
140 ~ 280N/cm of crushing strength, 0 ~ 2wt% of abrasion resistance, 240 ~ 600m of specific surface area2/ g, 0.30 ~ 1.00cm of pore volume3/ g, heap
Product 0.40 ~ 0.80g/cm of density3。
14. carrier according to claim 13, it is characterised in that: 1.2~3.0mm of Carrier diameters, crushing strength 160 ~
240N/cm, 300 ~ 480m of specific surface area2/ g, 0.40 ~ 0.80cm of pore volume3/g；0.50 ~ 0.70g/cm of bulk density3。
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| CN101468322A (en) * | 2007-12-27 | 2009-07-01 | 中国石油化工股份有限公司 | Alumina supporter and preparation method thereof |
| CN101590433A (en) * | 2008-05-29 | 2009-12-02 | 北京三聚环保新材料股份有限公司 | Modified aluminium oxide supports and the hydrogenation catalyst and the preparation method that make by this carrier |
| CN103787389A (en) * | 2012-11-01 | 2014-05-14 | 中国石油化工股份有限公司 | Production method of alumina carrier |
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- 2014-12-04 CN CN201410723785.5A patent/CN105642369B/en active Active
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|---|---|---|---|---|
| CN1209355A (en) * | 1997-08-27 | 1999-03-03 | 中国石油化工总公司 | Macroporous alumina supporter and preparation method therefor |
| CN1714937A (en) * | 2004-06-29 | 2006-01-04 | 中国石油化工股份有限公司 | Great pore volume formed aluminium oxide carrier and its preparing method |
| CN1762585A (en) * | 2005-09-30 | 2006-04-26 | 清华大学 | Preparation process of selective reduction catalyst for lean-burn gasoline motor car exhausted gas nitrogen oxide |
| CN101468322A (en) * | 2007-12-27 | 2009-07-01 | 中国石油化工股份有限公司 | Alumina supporter and preparation method thereof |
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