CN1448217A - Alumina supporter containing flurine and its preparing process - Google Patents
Alumina supporter containing flurine and its preparing process Download PDFInfo
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- CN1448217A CN1448217A CN 02109396 CN02109396A CN1448217A CN 1448217 A CN1448217 A CN 1448217A CN 02109396 CN02109396 CN 02109396 CN 02109396 A CN02109396 A CN 02109396A CN 1448217 A CN1448217 A CN 1448217A
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Abstract
The fluoride bearing alumina carrier consists of (accounting in the weight of catalyst): fluorine 0.5-15 wt%, assistant M 1.0-30 wt% and alunina the rest. Fluorine and assistant M are added during forming the alumina carrier in kneading mode. The said process can prepare carrier with F and M contents and F/M ratio adjustable within certain range and physical and chemical properties adjustable within certain range. The carrier can meet the requirement for various hydrogenating catalyst and features less loss of F inside the carrier.
Description
1, technical field
The present invention relates to a kind of fluoro-containing alumina carrier and preparation method thereof, particularly prepare used fluoro-containing alumina carrier of hydrogenation catalyst and preparation method thereof.
2, background technology
Aluminium oxide is a kind of common used in industry catalyst carrier, has been widely used in the preparation of industrial catalyst.But because there are some weakness in alumina support, as: a little less than the acidity, and mainly be L acid (Lewise acid), B acid (Br ō nsted acid) is then very weak; Easily form the species (for example easily and nickel formation nickel aluminate) of non-activity with hydrogenation activity component generation strong interaction, the sintering of active component or carrier easily takes place and influences many shortcomings such as activity of such catalysts, stability as catalyst carrier with aluminium oxide in simple.
Simple aluminium oxide has above-mentioned shortcoming, and also the character of catalyst carrier is proposed more specifically requirement at certain type reaction.According to the weakness of aluminium oxide and concrete reaction requirement, people adopt several different methods to improve the surface nature of alumina support, just can overcome above shortcoming effectively such as introduce the fluorine auxiliary agent in alumina support.All adopt the surface nature of improving aluminium oxide at alumina surface dipping fluorine auxiliary agent among patent CN1602090 and the CN1056514, improve support acidity and finally reach the purpose that improves catalyst hydrogenation activity.Adopt fluorine-containing solution to carry out isomorphous substitution reaction among patent US5129648 and the US5080778 and prepare silica-alumina supports of fluoridizing or the alumina support of fluoridizing, the metal component of load with hydrogenation activity makes catalyst then.Be carrier with silica and aluminium oxide mixed oxide among the patent US4427534, flood the hydrogenation activity that the fluorine auxiliary agent promotes tungsten and nickel component then, this catalyst has the saturated performance of higher hydrodesulfurization, hydrodenitrogeneration and aromatic hydrocarbons, is mainly used in the production of jet fuel and diesel oil.All adopt fluorine as auxiliary agent in the above patent, but all do not relate to the losing issue of fluorine, the loss of fluorine can produce following unfavorable result: 1. the reduction of fluorine content causes that activity of such catalysts descends, the fluorine corrosion upstream device that 2. runs off, and 3. the fluorine of Liu Shiing is taken out of with product and contaminated environment.
3, summary of the invention
The objective of the invention is alumina support is carried out modification, to satisfy the requirement of hydrogenation catalyst, being satisfied with particularly that oil hydrogenation in the petroleum refining industry is handled and the requirement of Hydrobon catalyst, more specifically is the fluoro-containing alumina carrier that a kind of fluorine of preparation is difficult for loss.
The invention discloses a kind of fluoro-containing alumina carrier and preparation method thereof, this carrier contains fluorine and a kind of auxiliary agent M.Wherein fluorine is to add to mix the mode of pinching, and adds auxiliary agent M in the same way, and said M is one or more among Si, Ti, Zr, the B.By fluorine in the carrier of this method preparation with M forms and the ratio of F/M can be adjusted within limits, the physico-chemical property of carrier can be adjusted within limits, can satisfy carrier, it is characterized in that fluorine is difficult for running off in this carrier as all kinds of hydrotreating catalysts of preparation.
The technology of the present invention feature is simultaneously alumina support to be carried out modification with fluorine and second kind of auxiliary agent M (M is one or more among Si (silicon), Ti (titanium), Zr (zirconium), the B (boron)), the second kind of auxiliary agent M that introduces in alumina support outside the defluorination not only can play the effect of adjusting catalyst carrier character, and can prevent the loss of fluorine in the catalyst carrier effectively, thereby the catalyst loss of fluorine in use causing catalyst activity reduction, environmental pollution, corrosion upstream device problem have been solved.
The introducing mode of fluorine and second kind of auxiliary agent M can be because of the preparation method of catalyst and carrier different the change, wherein in the body formed process of carrying alumina, introduce fluorine and auxiliary agent M and can play and simplify the catalyst carrier preparation process, have an effect that prevents that fluorine runs off in catalyst and the carrier simultaneously.
The preparation method of fluoro-containing alumina of the present invention:
Get aluminium oxide or aluminum hydroxide solid elastomer powder, add additive, water, peptizing agent, fluorochemical and contain the even aftershaping of compound of second kind of auxiliary agent M, drying then, roasting and make desired fluoro-containing alumina carrier.
By the fluoro-containing alumina carrier of the inventive method preparation, character is as follows:
Composition is a benchmark with the quality of catalyst, and mass percent is: fluorine 0.5～15m%, and M1.0～30m% (in oxide), all the other are aluminium oxide.Wherein M is one or more among Si, Ti, Zr, the B, and M is preferably Si, with SiO
2Form is calculated content and is preferably 2.0～15m%SiO
2
Pore structure character: pore volume 0.2～1.0ml/g, specific area 100～400m
2/ g
The acid amount of carrier, characterizes with infrared spectrum as probe molecule with pyridine, and the acid amount is: B acid 0.05～0.40mmol/g, L acid 0.1～0.35mmol/g.
Describe the preparation method of fluoro-containing alumina carrier of the present invention below in detail:
(1) taking by weighing required aluminum hydroxide solid elastomer powder and/or aluminum oxide dry glue powder and additive mixes;
(2) fluorochemical, peptizing agent and water are mixed with solution;
(3) compound that contains auxiliary agent M adds in the mixture of step (1) or in the solution of step (2) and mixes;
(4) material in the above step is mixed, on make-up machine, make catalyst carrier then, drying, roasting obtains the fluoro-containing alumina carrier.
The consumption of each material is a benchmark with the aluminium oxide butt in the Preparation of Catalyst, additive accounts for 2.0～15m%, fluorochemical accounts for 2.0～30m%, peptizing agent accounts for 1.0～10m%, the compound of auxiliary agent M (in pure compound) accounts for 1.0～40m%, water accounts for 50～70m% in whole mixture, deduct the water yield that moisture content contained in each material is required adding.
Described aluminum hydroxide solid elastomer powder mainly is meant boehmite and/or boehmite, and aluminium oxide is meant γ-Al
2O
3, η-Al
2O
3, θ-Al
2O
3Dry glue powder.
Described additive is different because of different forming methods, such as: sesbania powder, carbon black, graphite, citric acid, macromolecular organic compound (such as methylcellulose, cellulose acetate etc.), animal glue etc.The main purpose of adding these materials is to help moulding, improves the intensity of catalyst, improves the efficient of moulding, also may produce some other little effect simultaneously, the influence that the pore structure of catalyst carrier is produced microcosmic.
Described fluorochemical mainly is meant ammonium fluosilicate, ammonium fluoride, hydrofluoric acid etc., wherein be preferred with the ammonium fluosilicate, this raw material has following advantage: 1. the source of fluorine and silicon is provided simultaneously, and 2. ammonium fluosilicate is soluble in water, and the aqueous solution becomes acidity can partly or entirely replace peptizing agent.
Described peptizing agent can be an inorganic acid, as: nitrate, phosphoric acid, hydrofluoric acid etc., organic acid, as: formic acid, acetate, oxalic acid, citric acid etc., highly acid anion salt soluble in water, such as: aluminum nitrate, aluminum sulfate, ammonium fluosilicate etc.
Describedly contain the compound that second kind of auxiliary agent M compound mainly is meant one or more elements among Si (silicon), Ti (titanium), Zr (zirconium), the B (boron), wherein serve as preferred to contain Si (silicon) compound, silicon-containing compound can be that the inorganic compound of silicon is such as silica, Ludox, silicon gel etc.; The organic compound of silicon is such as silester, methyl silicate etc., and preferably adopting the Ludox of low sodium element is raw material.
The introducing mode that contains second kind of auxiliary agent M compound can be: 1. when containing second kind of auxiliary agent M compound and be solid state powder, aluminium hydroxide or aluminum oxide dry glue powder, contain the M compound and extrusion aid is mixed together evenly, and then add the mixed solution of fluorochemical and peptizing agent; 2. when containing second kind of auxiliary agent M compound and be water-soluble material, can get part water this compound dissolving, add then in the mixture in the step (1) that has mixed, or be mixed with mixed solution with fluorochemical containing second kind of auxiliary agent M compound, add then in the mixture in the step (1).
Described forming method mainly refers to industrial forming method commonly used, as extruded moulding, beat methods such as sheet (compressing tablet) moulding, spin.
Drying among the preparation method is between 80～130 ℃ dry 1～10 hour, and roasting is roasting 1～20 hour between 500～900 ℃.
Outside the defluorination auxiliary agent, following advantage is found in the introducing of second kind of auxiliary agent M at least: 1. can adjust the ratio of F/M, and the content of auxiliary agent M.The for example simple ammonium fluosilicate that only adds, the ratio of adjusting F/Si is very difficult, can finely tune the amount of F by raising sintering temperature or change time, but effect is undesirable, too high sintering temperature can make the part fluorine burn, simultaneously the pore structure of carrier must not produce influences, if add after the silicon compound, the ratio of F/Si is easy to adjust.2. introduce the loss that the compound that contains auxiliary agent M can prevent fluorine afterwards effectively.Fluorine is introduced into as the auxiliary agent of catalyst, can improve the character of catalyst significantly, but in use bring a series of problems because of the loss of fluorine owing to contain fluorine catalyst: fluorine runs off and causes the reduction of fluorine content, cause activity of such catalysts to descend, corrode the equipment, contaminated environment in downstream etc. after fluorine runs off.Adopt among the present invention to contain the method that the M compound is introduced second kind of auxiliary agent M, discovery can suppress the loss of fluorine effectively, thereby the loss that has solved fluorine causes problems such as catalyst activity reduction, corrosion upstream device, environmental pollution.3. introduce the pore structure character that second kind of auxiliary agent M can improve catalyst afterwards.In addition, simple employing ammonium fluosilicate, particularly during the large usage quantity of ammonium fluosilicate, the pore structure of alumina support is destroyed obviously, show that mainly pore volume reduces, specific area reduces, and introduces second kind of auxiliary agent M compound, the particularly introducing of Ludox, and Ludox prior to or simultaneously and ammonium fluosilicate join the effect that can effectively play reaming in aluminium oxide or the aluminium hydroxide together.
Adopt the fluoro-containing alumina carrier of the inventive method preparation to have good effect:
1) fluorine is difficult for running off in the carrier of making.2) in the carrier fluorine and M auxiliary agent form and the ratio of F/M can
Adjust within the certain limit.3) can be used as the catalyst carrier for hydrgenating that polytype reacts.
The ratio of F/M in the carrier can be adjusted because of the compound that adding contains M, and when second kind of auxiliary agent M was Si, the ratio of the amount of substance of fluorine silicon can be at F/Si=5～adjust between 0.30: 1.
The physico-chemical property of carrier mainly is meant the acidity of pore structure (comprising pore volume, specific area, aperture) and carrier.Its central hole structure character can be adjusted because of selecting different aluminium hydroxide or aluminum oxide dry glue powder source, also can change preparation condition, such as improving sintering temperature, adds expanding agent and meets the demands.Simple alumina support acidity a little less than, and mainly be L acid, and many catalyst carriers need certain B acid, strengthen the cracking activity of catalyst, by the fluoro-containing alumina carrier of the present invention's preparation, its acidity can be adjusted within limits, particularly can increase the concentration of B acid, as probe molecule, characterize the scope 0.05～0.40mmol pyridine/gram of this carrier B acid with infrared with pyridine.
The present invention has broad application prospects: after the carrier loaded certain VIB of fluoro-containing alumina (W, the Mo) family and VIII (Fe, Co, Ni) family hydrogenation activity component with the inventive method preparation, can be used as the hydrofinishing and the hydrotreating catalyst of all kinds of oil products.Comprising the Hydrobon catalyst of preparation distillate, the Hydrobon catalyst of heavy distillate, the Hydrobon catalyst of lubricating oil, the hydrotreating catalyst of residual oil.
4, the specific embodiment
Embodiment 1
With extruded moulding is the preparation process that example is introduced carrier.
Get Ludox 8.5ml (SiO
230m%), ammonium fluosilicate 10g and water 80ml are mixed with solution; Aluminium hydroxide dry powder 100g, carbon black 10g and sesbania powder 5.0g are mixed, add above-mentioned solution and be kneaded into uniform plastic, extruded moulding is the cloverleaf pattern bar of 1.2mm, 120 ℃ of dryings 4 hours, 600 ℃ of roasting temperatures 4 hours, can obtain the fluoro-containing alumina carrier A, experimental result and carrier character see Table 1.
Get ammonium fluosilicate 8.0g, acetum 1.0ml (36%) and water 85ml and be mixed with fluorine-containing solution; Aluminium hydroxide dry powder 100g, carbon black 10g and sesbania powder 5.0g are mixed, adding Ludox 7.0ml mixes, adds above-mentioned fluorine-containing solution and is kneaded into uniform plastic earlier, extruded moulding is the cloverleaf pattern bar of 1.2mm, 110 ℃ of dryings 4 hours, roasting is 4 hours under 600 temperature ℃ degree, can obtain the fluoro-containing alumina carrier B, the character of experimental result and carrier sees Table 1.
With aluminium hydroxide dry powder 100g and acetic acid 5.2ml, sesbania powder 5.0g and water 75ml are kneaded into uniform plastic, and extruded moulding is the cloverleaf pattern bar of 1.2mm, and 120 ℃ of dryings 4 hours 600 ℃ of roasting temperatures 4 hours, make alumina support; Ammonium fluoride 22g adds deionized water and is mixed with the 200ml aqueous solution, and this solution impregnation of carrying alumina body and function 4 hours, 110 ℃ of dryings 3 hours 600 ℃ of roasting temperatures 4 hours, made the fluoro-containing alumina support C, and the character of experimental result and carrier sees Table 1.
Get ammonium fluosilicate 8.0g and water 75ml is mixed with solution; Aluminium hydroxide dry powder 100g and sesbania powder 5.0g are mixed, add above-mentioned solution and be kneaded into uniform plastic, extruded moulding is the cloverleaf pattern bar of 1.2mm, 120 ℃ of dryings 4 hours, roasting is 4 hours under 600 temperature ℃ degree, can obtain fluoro-containing alumina carrier D, experimental result and carrier character see Table 1.
The character of table 1 fluoro-containing alumina carrier
*Annotate: the acid amount of carrier be with pyridine as probe molecule, infrared spectrum measurement result in the time of 250 ℃, unit is mmol pyridine/g.
Get ammonium fluosilicate 5.0g, acetum 2.0ml and water 80ml and be mixed with fluorine-containing solution; Aluminium hydroxide dry powder 100g, boric acid 4.5g, carbon black 10g and sesbania powder 5.0g are mixed, add fluorine-containing solution again and be kneaded into uniform paste plastic, extrusion modling is the column type bar of 1.5mm, 110 ℃ of dryings 3 hours, roasting is 3 hours under 650 temperature ℃ degree, get fluoro-containing alumina carrier E, experimental result and carrier character see Table 1.
Comparing embodiment
Get above-mentioned fluoro-containing alumina carrier A, B, C, D and heated 200 hours under 450 ℃ of temperature in air atmosphere, analyzed the variation before and after the fluorine content in the carrier is handled, experimental result is listed in the table 2.The fluorine turnover rate of support C and D illustrates in the fluoro-containing alumina carrier and adds after second kind of auxiliary agent far above the fluorine turnover rate of carrier A and B as can be seen from the experimental result of table 2, has prevented the loss of fluorine effectively.
Usually the serviceability temperature of hydrotreatment and Hydrobon catalyst is at 300～400 ℃, according to the climing empirical rule of Hough, 10 ℃ of the every raisings of reaction temperature, reaction speed is accelerated 2～4 times, therefore under 450 ℃ of temperature, fluorine loss reaction speed 100 times under the common catalyst serviceability temperature, the result that following 200 hours fluorine of 450 ℃ of temperature run off is equivalent to 2 years under the catalyst serviceability temperature at least.
The fluorine loss experimental result of table 2 fluoro-containing alumina carrier
Application Example
Present embodiment has been introduced the application of fluoro-containing alumina carrier, the preparation Hydrobon catalyst.
Get 33g nickel nitrate (Ni (NO
3)
26H
2O), the 52g ammonium metatungstate (contains WO
385.2%), is mixed with 100ml tungsten nickel solution after adding deionized water and stirring dissolving.The carrier A of getting among this tungsten nickel solution 40ml and the 50g embodiment 1 places rotary drum to spray, and the time of spraying is 30 minutes, has sprayed the back taking-up and has dried 3 hours down at 110 ℃, then 450 ℃ of following roastings 3 hours, makes catalyst, and it consists of: 24m%WO
3, 4.8m%NiO.The unifining process that can be used for distillate after this catalyst vulcanizes according to a conventional method.
Claims (11)
1, a kind of preparation method of fluoro-containing alumina carrier is characterized in that fluorine is to add to mix the mode of pinching, and adds auxiliary agent M in the same way that said M is one or more among Si, Ti, Zr, the B.
2, according to the described preparation method of claim 1, it is characterized in that comprising following steps:
(1) taking by weighing required aluminum hydroxide solid elastomer powder and/or aluminum oxide dry glue powder and additive mixes;
(2) fluorochemical, peptizing agent and water are mixed with solution;
(3) compound that contains auxiliary agent M adds in the mixture of step (1) or in the solution of step (2) and mixes;
(4) material in the above step is mixed, on make-up machine, make catalyst carrier then, drying, roasting obtains the fluoro-containing alumina carrier.
3. according to the described preparation method of claim 2, the consumption that it is characterized in that each material in the preparation process is a benchmark with the aluminium oxide butt: additive 2.0～15m%, fluorochemical 2.0～30m%, peptizing agent 1.0～10m%, compound 1.0～the 40m% that contains auxiliary agent M, water 50～70m%.
4,, it is characterized in that said fluorochemical refers to ammonium fluosilicate, ammonium fluoride and/or hydrofluoric acid in the step (2) according to the described preparation method of claim 2.
5,, it is characterized in that the said compound that contains auxiliary agent M refers to the compound of one or more elements among Si, Ti, Zr, the B according to the described preparation method of claim 2.
6,, it is characterized in that the said compound that contains auxiliary agent M refers to contain the Si compound according to claim 2 or 5 described preparation methods.
7,, it is characterized in that the said Si of containing compound is the inorganic compound of Si and/or the organic compound of Si according to the described preparation method of claim 6.
8,, it is characterized in that the inorganic compound of said Si is: silica, Ludox and/or silicon gel according to the described preparation method of claim 7; The organic compound of Si is silester and/or methyl silicate.
9, a kind of fluoro-containing alumina carrier by the described method preparation of claim 1, composition is a benchmark with the carrier quality: fluorine 0.5～15m%, M counts 1.0～30m% with oxide, and all the other are aluminium oxide, and wherein said M is one or more among Si, Ti, Zr, the B.
10, according to the described carrier of claim 9, it is characterized in that said M is Si, its content is with SiO
2Form is counted 2.0～15m%.
11, according to the described carrier of claim 9, it is characterized in that the rerum natura of said carrier is as follows: pore volume 0.2～1.0ml/g, specific area 100～400m
2/ g, the acid amount is: B acid 0.05～0.40mmol/g, L acid 0.1～0.35mmol/g.
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|---|---|---|---|
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|---|---|---|---|
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| CN1166455C CN1166455C (en) | 2004-09-15 |
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|---|---|---|---|
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| CN102061189A (en) * | 2009-11-11 | 2011-05-18 | 中国石油天然气股份有限公司 | Deep hydrogenation pretreatment method for heavy distillate oil |
| CN102794159A (en) * | 2011-05-27 | 2012-11-28 | 中国石油化工股份有限公司 | Fluorine-containing hydrated alumina forming composition and preparation method thereof |
| CN102861575A (en) * | 2011-07-07 | 2013-01-09 | 中国石油化工股份有限公司 | Shell catalyst and preparation method thereof |
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| CN102794159B (en) * | 2011-05-27 | 2014-12-31 | 中国石油化工股份有限公司 | Fluorine-containing hydrated alumina forming composition and preparation method thereof |
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| CN102861575B (en) * | 2011-07-07 | 2015-07-01 | 中国石油化工股份有限公司 | Shell catalyst and preparation method thereof |
| CN103041833B (en) * | 2011-10-17 | 2015-01-14 | 中国石油化工股份有限公司 | Aromatic hydrogenation saturation catalyst, preparation method thereof and aromatic hydrogenation catalytic method |
| CN103041804A (en) * | 2011-10-17 | 2013-04-17 | 中国石油化工股份有限公司 | Aromatic hydrogenation catalyst, preparation method thereof and aromatic hydrogenation catalytic method |
| CN103041831B (en) * | 2011-10-17 | 2014-12-31 | 中国石油化工股份有限公司 | Aromatic hydrogenation catalyst, preparation method thereof and aromatic hydrogenation catalytic method |
| CN103041804B (en) * | 2011-10-17 | 2014-12-31 | 中国石油化工股份有限公司 | Aromatic hydrogenation catalyst, preparation method thereof and aromatic hydrogenation catalytic method |
| CN103041832A (en) * | 2011-10-17 | 2013-04-17 | 中国石油化工股份有限公司 | Aromatic hydrogenation saturation catalyst, preparation method thereof and aromatic hydrogenation catalytic method |
| CN103041833A (en) * | 2011-10-17 | 2013-04-17 | 中国石油化工股份有限公司 | Aromatic hydrogenation saturation catalyst, preparation method thereof and aromatic hydrogenation catalytic method |
| CN103041832B (en) * | 2011-10-17 | 2015-06-17 | 中国石油化工股份有限公司 | Aromatic hydrogenation saturation catalyst, preparation method thereof and aromatic hydrogenation catalytic method |
| CN103041831A (en) * | 2011-10-17 | 2013-04-17 | 中国石油化工股份有限公司 | Aromatic hydrogenation catalyst, preparation method thereof and aromatic hydrogenation catalytic method |
| CN103801312A (en) * | 2012-11-08 | 2014-05-21 | 中国石油化工股份有限公司 | Preparation method for hydrotreatment catalyst |
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