CN103785368B - Clean binding agent and preparation method thereof - Google Patents
Clean binding agent and preparation method thereof Download PDFInfo
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- CN103785368B CN103785368B CN201210432664.6A CN201210432664A CN103785368B CN 103785368 B CN103785368 B CN 103785368B CN 201210432664 A CN201210432664 A CN 201210432664A CN 103785368 B CN103785368 B CN 103785368B
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Abstract
The present invention relates to a kind of clean binding agent and preparation method thereof, clean binding agent contains oxide precursor, organic acid and water, take quality as benchmark, the precursor content of oxide is 3% ~ 40%, it is characterized in that: organic acid and oxide mol ratio are 0.1:1 ~ 0.8:1; The crystal grain of oxide precursor is nanometer-size die, and crystal grain is less than 100nm.The preparation method of clean binding agent comprises (1) preparation organic acid soln, by adding appropriate deionized water in organic acid, stirs; In above-mentioned solution, slowly add the nano-oxide precursor of metering, stir; (2) ageing 2 ~ 15h, namely prepares clean binding agent.The present invention cleans binding agent and does not use inorganic acid, solves the pollution problem in production, can ensure the intensity of catalyst or catalyst carrier simultaneously.
Description
Technical field
The present invention relates to a kind of clean binding agent, especially a kind of not containing catalyst carrier or the shaping of catalyst organic acid binding agent of nitrate anion.
Background technology
The geometric shape of catalyst and physical dimension, have impact to fluid resistance, air velocity, the distribution of bed temperature gradient, concentration gradient distribution etc.In order to give full play to its catalysis potentiality, should select optimum profile and size, this just needs to select most suitable forming method.Shaping of catalyst technology mainly comprises spray shaping, forming oil column, extruded moulding, compression molding and rotational forming etc.The material that normally can form gel in the selection principle of shaping of catalyst method can make microballoon or bead, and the good mucilage of plasticity or the easy extrusion of powder or compressing tablet, malleable metal or alloy is woven into silk screen sometimes.Wherein extruded moulding technology is most widely used, especially the hydrogen addition technology field of oil refining industry.Need to add a certain amount of binding agent or diluted acid peptizing agent in extruded moulding process, cementation is played in effect, ensures that shaping rear catalyst has certain geometry appearance shape and higher withstand voltage, scuff resistance.The preparation of binding agent, mainly by diluted acid and the dry glue of oxide Homogeneous phase mixing according to a certain percentage, obtains jelly through stirring, precipitation.Along with the development of catalyst preparation technology, binding agent obtains increasing attention in the effect of shaping of catalyst process.
In catalyst or carrier extruded moulding process, binding agent adopts mixing jelly such as the CN93117528.3 of the oxide that acid stronger non-volatile inorganic is sour and pore volume is less to adopt the inorganic oxide of aluminium oxide, titanium oxide, silica and clay or inorganic matter oxide mixture and inorganic acid to prepare binding agent usually.Patent US8,021,540 adopt inorganic matter powdered components as shaping of catalyst binding agent, as clay, imvite, waterglass etc., and US7,687,676 directly use mineral acid acidified Ludox or Alumina gel as the binding agent in shaping of catalyst process.The effect of binding agent is that after the various component Homogeneous phase mixing by catalyst or carrier, peptization becomes the paste shape that can squeeze, and (banded extruder) carries out extruded moulding at elevated pressures, then carries out drying and high-temperature roasting process.In drying and roasting process, biochemical reaction is issued in the effect of strong acid and little orifice oxide between the contact interface of each component, form the staggered chemical bond be connected each other, thus make catalyst or carrier have certain geometric shape and very high withstand voltage, scuff resistance.Wherein the effect of little orifice oxide not easily interacts in catalyst or carrier between the larger component of pore volume, plays the effect of connection or grafting, make it combine closely each other, improve the mechanical strength of shaping rear catalyst or carrier.Therefore, the acids used as catalyst or carrier molding adhesive needs to have stronger acidity, and noresidue after decomposes; The little pore volume oxide used then needs to have less granularity, pore volume, and relatively large bulk density.
Nitric acid has acid strong, easy decomposition, price is low, and the advantage such as noresidue in the catalyst after decomposing, prepare the inorganic acid that hydrocracking catalyst the most often uses, and the maximum medium and small orifice oxide of binding agent of industrial application usually adopt adhesive property good, prepare easy γ-little porous aluminum oxide precursor.CN97121663.0 gives a kind of beta-zeolite molecular sieve catalyst and preparation method thereof, and the binding agent using the aluminium oxide precursor (boehmite) of nitric acid and little pore volume to prepare in the preparation process of catalyst, obtains good effect.But decomposes is discharged a large amount of NO by nitric acid in follow-up roasting process
x, causing suitable environmental hazard, is one of key factor of restriction Catalyst Production link.NO
xbeing a kind of main atmospheric pollutant, is form one of acid rain, photochemical fog and the primary pollution source causing ozone hole.In addition, a large amount of NO
xgeneration also can cause heavy corrosion to production equipment and very big infringement be caused to operator ' s health.
Increasingly strict along with environmental law, solves the NO in catalyst preparation process
xpollution problem more and more receives concern.In order to cleaning of catalyst production process, people have selected some clean raw material without ammonia nitrogen discharge in catalyst preparation process.Therefore, in shaping of catalyst process nitric acid alternative acids be selected to the problem that receives publicity.CN00110016.5 and CN00123221.5 describes two kinds of oil refining class loaded catalyst extruded moulding methods respectively.In the selection of Aci-Jel solvent, except nitric acid can be used as Aci-Jel solvent, two schemes all have employed more inorganic and organic acid and selects, as inorganic acid can select the combination of phosphoric acid, hydrochloric acid, sulfuric acid or several acid, organic acid can formic acid, acetic acid, oxalic acid, citric acid etc.But all there is the impurities left problems such as Cl, S, P after these inorganic acid decomposes, be not suitable as the peptizing agent of shaping of catalyst; Organic acid is then because its acidity is more weak be difficult to the requirement meeting preparation high strength catalyst.
Nano material, owing to having small-size effect, skin effect, quantum effect etc., can give material itself a series of good characteristic.As having during catalysis material that particle size is little, specific area is large, surface-active high, its catalytic activity and selective far away higher than traditional catalyst, demonstrates the excellent specific property that many traditional catalyst are incomparable.In addition, nanocatalyst also shows the performance such as excellent electro-catalysis, magnetic catalysis.Therefore, nano material has been widely used in many fields such as oil, chemical industry, the energy, coating, biology and environmental protection.Gama-alumina is widely used as catalyst carrier in oil refining, petrochemical industry and chemical fertilizer industry and drier, adsorbent etc. owing to having large specific area and good heat endurance.Nanoscale gama-alumina has the features such as specific area is larger, acidity is stronger, surface hydroxyl is active, and it receives increasing concern in the application of catalytic field.The preparation method of current alumina in Nano level has a variety of, such as micro emulsion method, ultrasonic wave-chemical precipitation method, combustion method, sol-gel process, aluminum nitrate and hexogen mixing Detonation Process etc.CN201010587691.1 and CN201110146441.9 sets forth the method preparing nano aluminium oxide, all can adopt comparatively simple preparation technology's flow process, prepare low impurity, good dispersion, hard aggregation-free high-performance nano alumina product at low cost.
Summary of the invention
For the deficiencies in the prior art, the present invention selects organic acid as sour peptizing agent, select a kind of nano-scale oxide precursor material as the aperture inorganic oxide component of binding agent, compared with the little orifice oxide precursor of routine, the bond properties of binding agent can be strengthened, prepare the clean binding agent of catalyst or the catalyst carrier that may be used for production high strength.The present invention also provides the preparation method of above-mentioned clean binding agent.
The present invention cleans binding agent and contains oxide precursor, organic acid and water, take quality as benchmark, and the precursor content of oxide is 3% ~ 40%, and preferably 8% ~ 25%, organic acid and oxide mol ratio are 0.1:1 ~ 0.8:1, are preferably 0.15:1 ~ 0.7:1; The crystal grain of oxide precursor is nanometer-size die, and crystal grain is less than 100nm, is preferably 20 ~ 40nm.
The present invention cleans in binding agent, and oxide precursor is generally one or more in aluminium oxide precursor, silica precursor, magnesia precursor, amorphous aluminum silicide precursor etc., is preferably aluminium oxide precursor.Aluminium oxide precursor is generally nanoscale boehmite, and silica precursor is generally nano silicone colloidal sol, and magnesia precursor is nanometric magnesium hydroxide, and amorphous aluminum silicide precursor is nano-scale amorphous sial dry glue powder.Above-mentioned nanoscale material can adopt commercially available prod, also can by the existing method preparation in this area.The pore volume <0.4mL/g of oxide precursor, surface area >320m
2/ g.
The present invention cleans in binding agent, and organic acid can be the mixture of one or more of formic acid, acetic acid, ethanedioic acid, citric acid, acetic acid.The mol ratio of organic acid and oxide refers to, when oxide precursor is with oxide basis, and the mol ratio of organic acid and oxide.
The present invention cleans in binding agent, also can add other additive as required, as extrusion aid, expanding agent etc.
The preparation process of binding agent of the present invention comprises following content:
(1) prepare organic acid soln, add appropriate deionized water by organic acid (formic acid, acetic acid, ethanedioic acid, citric acid, acetic acid one or more), stir;
(2) in above-mentioned solution, slowly add the nano-oxide precursor of metering, stir;
(3) ageing 2 ~ 15h, namely prepares clean binding agent.
In the above-mentioned preparation method of the present invention, when organic acid is water-soluble, heating for dissolving mode can be adopted, to improve dissolution velocity, as dissolved at 50 ~ 80 DEG C.Then mix with nano-oxide precursor under solution temperature or under being down to normal temperature.Ageing can be carried out at normal temperatures, also can carry out at 30 ~ 60 DEG C.
The present invention is directed to the NOx pollution problem of catalyst preparation process, select the organic acid cleaning and remain without ammonia nitrogen discharge, free from admixture as Aci-Jel solvent, the introducing of nitrate anion pollution sources is eliminated from source, prepare organic acid binding agent, the preparation process adopting extruded moulding catalyst and catalyst carrier can be widely used in.
Under the clean catalyst preparing without NOx emission requires, for improving the performance of organic acid binding agent, on the one hand can be acid by improving it, strengthen the adhesion between catalytic component; On the other hand, can by reducing the size of oxide precursor particulate in binding agent, to make between each component particles of catalyst or carrier distance each other shorter, strengthen its Van der Waals force each other or chemical bond power, thus improve the mechanical strength of catalyst or carrier.The present invention adopts a kind of nano-oxide precursor material substitution conventional oxide material, obtains the binding agent of a kind of clean catalyst or carrier preparation use.
The present invention, by selecting nano level little orifice oxide precursor as the oxide component of binding agent, increases the contact area of little orifice oxide and other component of catalyst, reduces the distance between component, enhance active force each other.The present invention selects nano level oxide precursor, makes more easily chemical action to occur between oxide precursor and organic acid, enhances the bond properties of binding agent, thus compensate for the acid weak point not strong compared with weakly caking performance of organic acid.The small nano-size pores oxide that the present invention selects is commercially available prod, and it is comparatively easy to obtain.
Preparation method of the present invention is simple, be easy to operation, can green, low-carbon (LC), environmental protection, prepare the preparation process being suitable for various extruded moulding catalyst or carrier efficiently, special-less process requirement, on the basis increasing ultrasonic wave sound source, utilize on existing equipment and just can realize whole production.
Detailed description of the invention
A kind of concrete preparation process of binding agent of the present invention is as follows:
1) prepare organic acid soln, weigh 660g oxalic acid (ethanedioic acid) white crystal, be dissolved in the distilled water of 50 DEG C of constant temperature stirrings, stir 20 minutes, make transparent 5000mL organic acid mixed solution, pH value is ~ 1.1.
2) take the little porous aluminum oxide precursor 720g that butt is 72.2%, be placed in ceramic whiteware mortar.Little porous aluminum oxide precursor is commercially available small nano-size pores boehmite, pore volume 0.36mL/g, and crystal grain is that 30 ~ 50nm(calculates according to XRD), specific area 410m
2/ g, bulk density 0.51g/cm
3, granularity is less than 200 orders.
3) the organic acid soln 1265mL measured in step 1 slowly joins in the mortar placing little porous aluminum oxide precursor, after static 20min, stirs, and become white translucent paste shape, standing at room temperature ageing 8h, can use.
Example 1(contrasts scheme)
Get 1280mL dilute nitric acid solution (concentration is 4.0g nitric acid/100mL), (crystal grain >300nm, butt is 72.5%, pore volume 0.32mL/g, specific area 286m to add the conventional aperture boehmite of 720g gradually
2/ g, bulk density ~ 0.62g/cm
3, granularity is less than 180 orders), after static 20min, stir, become white translucent paste shape, standing at room temperature ageing 8h, binding agent-1.
Example 2(contrasts scheme)
Example 1 dilute nitric acid solution is changed to acetic acid solution (concentration is 13.2g acetic acid/100mL), other, with example 1, prepares binding agent-2.
Example 3(contrasts scheme)
Example 1 dilute nitric acid solution is changed to citric acid solution (concentration is 18.8g citric acid/100mL), other, with example 1, prepares binding agent-3.
Example 4(contrasts scheme)
Conventional for example 1 aperture boehmite is replaced with nano level aperture boehmite (character is see detailed description of the invention part), other is with example 1, and preparing binding agent is binding agent-4.
Example 5(the present invention program)
Conventional for example 2 aperture boehmite is replaced with nano level aperture boehmite (character is see detailed description of the invention part), other, with example 2, prepares binding agent-5.
Example 6(the present invention program)
Conventional for example 3 aperture boehmite is replaced with nano level aperture boehmite, and other, with example 3, prepares binding agent-6.
Example 7(contrasts scheme)
The acetic acid solution concentration of example 5 is increased to 26.4g acetic acid/100mL, and other is with example 5, numbering binding agent-7.
Binding agent prepared by example 1 ~ 7, adopt the components such as the macroporous aluminium oxide of identical type and ratio to prepare a kind of hydrofining catalyst carrier, after super-dry and roasting, numbering is respectively S-1 ~ S-7, and wherein S-7 pulverizes substantially.Carrier S-1 be impregnated in molybdenum nickel phosphorus solution with S-5 and carry out supersaturation dipping, then 500 DEG C of roasting 3h, carrier and catalyst property see attached list.
| Carrier | S BET(m 2/g) | V single(cm 3/g) | R BET(nm) | Intensity, N/cm | Abrasion, % |
| S-1 | 324 | 0.612 | 7.4 | 210 | 0.8 |
| S-2 | 335 | 0.620 | 8.2 | 126 | 1.4 |
| S-3 | 344 | 0.628 | 8.0 | 117 | 1.9 |
| S-4 | 344 | 0.606 | 7.4 | 237 | 0.7 |
| S-5 | 358 | 0.612 | 7.8 | 201 | 0.9 |
| S-6 | 366 | 0.600 | 7.9 | 189 | 1.2 |
| Cat-1 | 210 | 0.323 | 5.7 | 215 | 0.7 |
| Cat-5 | 256 | 0.311 | 5.8 | 210 | 0.6 |
R
bETfor the average pore diameter that BET method records.
Strength detection, ZQJ-II Intelligent testing machine for particle (production of Dalian device diagnostic device factory).
Claims (6)
1. a clean binding agent, containing oxide precursor, organic acid and water, take quality as benchmark, the precursor content of oxide is 3% ~ 40%, it is characterized in that: organic acid and oxide mol ratio are 0.1:1 ~ 0.8:1; The crystal grain of oxide precursor is nanometer-size die, crystal grain is less than 100nm, described oxide precursor is one or more in aluminium oxide precursor, silica precursor, magnesia precursor and amorphous aluminum silicide precursor, and organic acid is the mixture of one or more of formic acid, acetic acid, ethanedioic acid, citric acid, acetic acid.
2. clean binding agent according to claim 1, is characterized in that: in clean binding agent, the precursor content of oxide is 8% ~ 25%.
3. clean binding agent according to claim 1, is characterized in that: organic acid and oxide mol ratio are 0.15:1 ~ 0.7:1.
4. clean binding agent according to claim 1, is characterized in that: the crystal grain of oxide precursor is 20 ~ 40nm.
5. clean binding agent according to claim 1, it is characterized in that: aluminium oxide precursor is nanoscale boehmite, silica precursor is nano silicone colloidal sol, and magnesia precursor is nanometric magnesium hydroxide, and amorphous aluminum silicide precursor is nano-scale amorphous sial dry glue powder.
6. a preparation method for clean binding agent according to claim 1, is characterized in that comprising the steps:
(1) preparing organic acid soln, by adding appropriate deionized water in organic acid, stirring;
In above-mentioned solution, slowly add the nano-oxide precursor of metering, stir;
(3) ageing 2 ~ 15h, namely prepares clean binding agent.
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| CN102000599A (en) * | 2010-11-09 | 2011-04-06 | 中国海洋石油总公司 | Preparation method of catalyst for deeply desorbing trace olefins in aromatic hydrocarbon |
| CN102294222A (en) * | 2010-06-24 | 2011-12-28 | 中国石油化工股份有限公司 | Hydrocarbon oil desulfurization adsorbent and preparation method and application thereof |
| CN102463131A (en) * | 2010-11-04 | 2012-05-23 | 中国石油化工股份有限公司 | Hydrocracking catalyst and preparation method thereof |
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| CN102294222A (en) * | 2010-06-24 | 2011-12-28 | 中国石油化工股份有限公司 | Hydrocarbon oil desulfurization adsorbent and preparation method and application thereof |
| CN102463131A (en) * | 2010-11-04 | 2012-05-23 | 中国石油化工股份有限公司 | Hydrocracking catalyst and preparation method thereof |
| CN102000599A (en) * | 2010-11-09 | 2011-04-06 | 中国海洋石油总公司 | Preparation method of catalyst for deeply desorbing trace olefins in aromatic hydrocarbon |
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