CN113562752B - Phosphorus-containing pseudo-boehmite, preparation method thereof, phosphorus-containing alumina and application thereof - Google Patents

Phosphorus-containing pseudo-boehmite, preparation method thereof, phosphorus-containing alumina and application thereof Download PDF

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CN113562752B
CN113562752B CN202010352291.6A CN202010352291A CN113562752B CN 113562752 B CN113562752 B CN 113562752B CN 202010352291 A CN202010352291 A CN 202010352291A CN 113562752 B CN113562752 B CN 113562752B
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phosphorus
boehmite
pseudo
peak
alumina
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CN113562752A (en
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曾双亲
杨清河
桑小义
刘滨
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
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Abstract

The invention relates to the field of pseudo-boehmite preparation, and discloses phosphorus-containing pseudo-boehmite, a preparation method thereof, phosphorus-containing alumina and application thereof, wherein h of the pseudo-boehmite is more than or equal to 1.7 and less than or equal to 3, h=D (031)/D (020), D (031) represents the grain size of a crystal face represented by 031 peak in an XRD spectrogram of pseudo-boehmite crystal grains, D (020) represents the grain size of a crystal face represented by 020 peak in the XRD spectrogram of pseudo-boehmite crystal grains, 031 peak is a peak with 2 theta of 34-43 DEG in the XRD spectrogram, 020 peak is a peak with 2 theta of 10-15 DEG in the XRD spectrogram, D=Klambda/(Bcostheta), K is a Scherrer constant, lambda is the diffraction wavelength of a target material, B is the half-peak width of the diffraction peak, and 2 theta is the position of the diffraction peak. Compared with the prior art, the phosphorus-containing pseudo-boehmite provided by the invention has the characteristic that h is more than or equal to 1.7 and less than or equal to 3, so that the phosphorus-containing pseudo-boehmite calcined phosphorus-containing alumina is more suitable for being used as a residual oil hydrogenation catalyst carrier, and the obtained catalyst has more excellent hydrodesulfurization performance.

Description

Phosphorus-containing pseudo-boehmite, preparation method thereof, phosphorus-containing alumina and application thereof
Technical Field
The invention relates to the field of pseudo-boehmite preparation, in particular to phosphorus-containing pseudo-boehmite, a preparation method thereof, phosphorus-containing alumina and application thereof.
Background
Alumina, particularly gamma-alumina, is often used as a support for catalyst preparation due to its relatively good pore structure, specific surface area and heat stability. The precursor of alumina is hydrated alumina, such as pseudo-boehmite, and the particle size, morphology, crystallinity, impurity crystal content and the like of the alumina carrier have influence on the properties of pore volume, pore distribution, specific surface area and the like. In the prior art, alumina carriers meeting specific requirements can be obtained by modulating the properties of particle size, morphology, crystallinity and the like of hydrated alumina.
Pseudo-boehmite as a raw material for alumina carriers is generally prepared by the following method: (1) alkali precipitation, i.e., neutralization of the acidified aluminum salt with alkali. Precipitating alumina monohydrate from the acidified aluminum salt solution with a base, and then aging, washing, drying and the like to obtain a pseudo-boehmite product, which is commonly called as a base precipitation (acid method), such as a method for neutralizing aluminum trichloride with ammonia water; (2) Acid precipitation, i.e. neutralization of aluminates with strong acids or aluminium salts of strong acids. The acid is used to precipitate alumina monohydrate from aluminate solution, then the pseudo-boehmite product is obtained through the processes of aging, washing, drying and the like, and the method is commonly called acid precipitation (alkaline method) and comprises the following steps: CO 2 A method for neutralizing sodium metaaluminate by gas, and a method for neutralizing sodium metaaluminate by aluminum sulfate; (3) The hydrolysis of alkoxy aluminium is carried out on the alkoxy aluminium and water to generate alumina monohydrate, and then the alumina monohydrate is aged, filtered and dried to obtain the pseudo-boehmite product. The preparation process of pseudo-boehmite generally comprises the processes of grain formation (neutralization precipitation or hydrolysis process), grain growth (aging process), washing, drying and the like. Therefore, the process conditions of grain generation and grain growth can influence the quantity and growth speed of grain generation, the preparation process of various pseudo-boehmite provides respective process conditions, and the grain size and crystallinity of the product are controlled so as to achieve the purpose of controlling the physical properties of the product, such as pore volume, specific surface area and the like.
The pore structure, surface acidity and thermal stability of the carrier can be changed by introducing phosphorus into the alumina, so that the activity of the hydrogenation catalyst can be improved.
The method is that firstly pseudo-boehmite powder is used for preparing an alumina carrier through molding and roasting, and then phosphorus is introduced into the alumina carrier through an impregnation method to prepare phosphorus modified alumina. The heat stability of the alumina can be improved by adopting an impregnation method to prepare phosphorus modified activated alumina, but the alumina is impregnated by phosphoric acid, part of the alumina is dissolved in phosphoric acid solution and reacts with phosphate to generate aluminum phosphate, and the aluminum phosphate is deposited in alumina pore channels and can block the pore channels, so that the specific surface area and the pore volume are reduced.
One method is to add a phosphorus-containing compound during the molding of pseudo-boehmite, followed by calcination of the molded compound to produce phosphorus-modified alumina. CN103721732a discloses a phosphorus-added modified pseudo-boehmite catalyst carrier material and a preparation method. Adding an aluminum sulfate solution with the alumina concentration of 45-55g/L and a sodium metaaluminate solution with the alumina concentration of 200-250g/L and the caustic ratio of 1.1-1.3 into a neutralization reaction kettle 1, controlling the pH value to be 6.0-8.0 and the temperature to be 50-70 ℃; the slurry of the neutralization reaction kettle 1 flows into the neutralization reaction kettle 2 through an overflow reaction pipe, and sodium carbonate solution with the concentration of 100-200g/L is added into the neutralization reaction kettle 2, the pH value is controlled to be 8.5-10.0, and the reaction temperature is controlled to be 50-70 ℃; the slurry in the neutralization reaction kettle 2 flows into an aging reaction kettle through an overflow reaction pipe, the temperature of the slurry in the aging reaction kettle is 80-95 ℃, and the aging is carried out for 2 hours; according to the mass of the alumina added in the reaction process of the neutralization reaction kettle 1, calculating the volume of a phosphoric acid solution with the phosphorus pentoxide concentration of 50-150g/L added into the aging reaction kettle, wherein the phosphorus pentoxide content of the added phosphoric acid is 3-5% of the alumina content; and (5) washing and drying after the aging is finished to obtain the phosphorus-containing pseudo-boehmite.
Although the above documents disclose various methods for producing phosphorus-containing pseudo-boehmite, and the properties of the pseudo-boehmite obtained are excellent in some respects, the properties of the catalyst are still further improved when the alumina produced therefrom is used as a catalyst support.
Disclosure of Invention
The invention aims to overcome the defect that the hydrodesulfurization performance of a catalyst needs to be further improved when aluminum oxide prepared from pseudo-boehmite in the prior art is used as a catalyst carrier, and provides phosphorus-containing pseudo-boehmite, a preparation method thereof, phosphorus-containing aluminum oxide and application thereof. The catalyst obtained by adopting the carrier prepared from the phosphorus-containing pseudo-boehmite has better hydrodesulfurization performance.
The inventor of the present invention found in the course of research that in the course of preparation of pseudo-boehmite, by adding a phosphorus-containing compound to the raw material, adding a grain growth regulator in the course of precipitation reaction or hydrolysis reaction, and controlling the pH of the precipitation reaction or hydrolysis reaction to be 4-7, and then adjusting the pH to be 7-10.5 for aging, the adjustment of the grain growth mode is enhanced, so that a phosphorus-containing pseudo-boehmite product with h being less than or equal to 1.7 and less than or equal to 3, preferably 1.9 and less than or equal to 3, more preferably 2.2 and less than or equal to 2.8 can be prepared, and the hydrodesulfurization performance of a catalyst using alumina obtained after calcination of the phosphorus-containing pseudo-boehmite as a carrier can be effectively improved. The phosphorus-containing pseudo-boehmite prepared by the prior art is generally 0.85-1.65 because h is not controlled. The pseudo-boehmite of the invention has the characteristic that h is less than or equal to 1.7 and less than or equal to 3, preferably less than or equal to 1.9 and less than or equal to 3, more preferably less than or equal to 2.2 and less than or equal to 2.8, so the pseudo-boehmite can improve the hydrogenation performance of the catalyst when used as a precursor of a carrier of the hydrogenation catalyst.
In order to achieve the above object, a first aspect of the present invention provides a phosphorus-containing pseudo-boehmite, h of which satisfies 1.7.ltoreq.h.ltoreq.3, wherein h=d (031)/D (020), D (031) represents a crystal grain size of a crystal plane represented by a 031 peak in an XRD spectrum of pseudo-boehmite crystal grains, D (020) represents a crystal grain size of a crystal plane represented by a 020 peak in an XRD spectrum of pseudo-boehmite crystal grains, said 031 peak means a peak in which 2θ is 34 to 43 °, said 020 peak means a peak in the XRD spectrum in which 2θ is 10 to 15 °, d=kλ/(bcosθ), K is Scherrer constant, λ is a diffraction wavelength of a target material, B is a half-width of a diffraction peak, and 2θ is a position of the diffraction peak.
Preferably, h of the pseudo-boehmite satisfies 1.9.ltoreq.h.ltoreq.3, preferably 2.2.ltoreq.h.ltoreq.2.8.
The second aspect of the invention provides a method for preparing phosphorus-containing pseudo-boehmite, which comprises the following steps:
(1) The inorganic aluminum-containing compound solution is contacted with acid or alkali to carry out precipitation reaction, or the organic aluminum-containing compound is contacted with water to carry out hydrolysis reaction, so as to obtain hydrated alumina containing phosphorus;
(2) Aging the obtained hydrated alumina containing phosphorus at pH 7-10.5;
the precipitation reaction or the hydrolysis reaction of the step (1) is carried out in the presence of a grain growth regulator and a phosphorus-containing compound at a pH of 4 to 7; the grain growth regulator is a substance capable of regulating the growth rate of grains on different crystal planes.
In a third aspect, the present invention provides a phosphorus-containing alumina obtained by calcining phosphorus-containing pseudo-boehmite, wherein the phosphorus-containing pseudo-boehmite is the phosphorus-containing pseudo-boehmite according to the first aspect or the phosphorus-containing pseudo-boehmite obtained by the method according to the second aspect.
In a fourth aspect, the present invention provides a phosphorus-containing alumina having an IR spectrum of (I) 3670 +I 3580 )/(I 3770 +I 3720 ) 1.9-2.8, wherein I 3670 3670cm -1 Peak height, I 3580 3580cm -1 Peak height, I 3770 3770cm -1 Peak height, I 3720 3720cm -1 Peak height.
In a fifth aspect the present invention provides the use of the phosphorus containing alumina of the preceding third or fourth aspect in hydrodesulphurisation.
Compared with the prior art, the phosphorus-containing pseudo-boehmite provided by the invention has the characteristic that h is more than or equal to 1.7 and less than or equal to 3, so that the phosphorus-containing pseudo-boehmite calcined phosphorus-containing alumina is more suitable for being used as a residual oil hydrogenation catalyst carrier, and the obtained catalyst has more excellent hydrodesulfurization performance. According to the preparation method of the phosphorus-containing pseudo-boehmite, provided by the invention, the phosphorus-containing compound, the grain growth regulator and the sectional control of the pH value in the preparation process are added, so that the obtained pseudo-boehmite has the characteristic that h is more than or equal to 1.7 and less than or equal to 3. The phosphorus-containing aluminum oxide obtained by roasting the phosphorus-containing pseudo-boehmite has specific surface hydroxyl group distribution, and in the IR spectrogram of the phosphorus-containing aluminum oxide, (I) 3670 +I 3580 )/(I 3770 +I 3720 ) 1.9 to 2.8; wherein I is 3670 3670cm -1 Peak height, I 3580 3580cm -1 Peak height, I 3770 3770cm -1 Peak height, I 3720 3720cm -1 The peak is high, the catalyst is more suitable for being used as a catalyst carrier, and the obtained catalyst has more excellent residual oil hydrodesulfurization performance. For example, residual oil hydrodesulfurization catalyst prepared by taking phosphorus-containing alumina obtained by roasting phosphorus-containing pseudo-boehmite prepared in example 1 of the invention as a carrier is subjected to LHSV for 0.50 hours at a reaction temperature of 380 DEG C -1 Residual oil desulfurization performance experiments were conducted under conditions of a hydrogen partial pressure of 14.0 mpa and a hydrogen oil volume ratio of 600, and the sulfur content of the obtained product was 0.48 wt%, while in the case of the hydrodesulfurization catalyst using the phosphorus-containing alumina calcined in the phosphorus-containing pseudo-boehmite prepared in comparative example 3 as a carrier, the sulfur content of the obtained product was 0.76 wt% and 36.8 wt% lower than the former.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The first aspect of the invention provides a phosphorus-containing pseudo-boehmite, h of which is 1.7-3, wherein h=d (031)/D (020), wherein D (031) represents a crystal grain size of a crystal plane represented by 031 peak in an XRD spectrum of pseudo-boehmite crystal grains, D (020) represents a crystal grain size of a crystal plane represented by 020 peak in an XRD spectrum of pseudo-boehmite crystal grains, 031 peak is a peak of 34-43 DEG in the XRD spectrum, 020 peak is a peak of 10-15 DEG in the XRD spectrum, d=Kλ/(Bcosθ), K is Scherrer constant, λ is a diffraction wavelength of a target material, B is a half-width of the diffraction peak, and 2θ is a position of the diffraction peak.
In the present invention, for different diffraction peaks, B and 2θ each take the value of the corresponding peak, for example, when D (031) is calculated, D (031) =kλ/(Bcos θ), where B is the half-peak width of the 031 diffraction peak and 2θ is the position of the 031 diffraction peak; when D (020) is calculated, D (020) =kλ/(bcosθ), where B is the half-width of the 020 diffraction peak and 2θ is the position of the 020 diffraction peak.
Preferably, h of the pseudo-boehmite is 1.9-3, more preferably 2.2-2.8. Within this preferred range, the resulting catalyst exhibits better hydrodesulfurization performance.
h, the phosphorus-containing aluminum oxide prepared by baking the phosphorus-containing pseudo-boehmite meeting the specification has specific hydroxyl distribution, and is more beneficial to improving the desulfurization performance of the catalyst. In the pseudo-boehmite prepared by the prior art, h is generally 0.85-1.65.
The relative crystallinity of pseudo-boehmite provided by the invention (based on commercial SB powder from Condea company) is generally in the range of 45-77%, preferably 65-77%.
The pseudo-boehmite provided by the invention contains phosphorus element, preferably, based on the total dry basis of the pseudo-boehmite, al 2 O 3 The content of (2) is 94-99 wt%, preferably 95-98 wt%; p (P) 2 O 5 The content of (2) is 1 to 6% by weight, preferably 2 to 5% by weight.
In the present invention, the crystal structure of pseudo-boehmite was measured using a D5005X-ray diffractometer from Siemens, germany, with a CuK alpha radiation of 44 kv, 40 mA, and a scanning speed of 2℃per minute.
The phosphorus-containing pseudo-boehmite provided by the invention contains phosphorus elements and has a specific crystal structure, and the catalyst containing the carrier prepared from the phosphorus-containing pseudo-boehmite provided by the invention shows excellent hydrodesulfurization performance.
The second aspect of the invention provides a method for preparing phosphorus-containing pseudo-boehmite, which comprises the following steps:
(1) The inorganic aluminum-containing compound solution is contacted with acid or alkali to carry out precipitation reaction, or the organic aluminum-containing compound is contacted with water to carry out hydrolysis reaction, so as to obtain hydrated alumina containing phosphorus;
(2) Aging the obtained hydrated alumina containing phosphorus at pH 7-10.5;
The precipitation reaction or the hydrolysis reaction of the step (1) is carried out in the presence of a grain growth regulator and a phosphorus-containing compound at a pH of 4 to 7; the grain growth regulator is a substance capable of regulating the growth rate of grains on different crystal planes.
In the method provided by the invention, the precipitation reaction or the hydrolysis reaction is carried out under the condition that the pH value is 4-7 in the presence of the grain growth regulator and the phosphorus-containing compound, so that the precipitation of phosphorus-containing hydrated alumina can be met, the lower pH value condition is maintained, the overquick growth of pseudo-boehmite grains under high pH value is avoided, and the common regulation effect of phosphorus and the growth regulator on the pseudo-boehmite growth is enhanced. The grain growth of pseudo-boehmite in the whole process of hydrated alumina generation and aging is carried out in the presence of phosphorus-containing compounds and grain regulators, so that the prepared pseudo-boehmite has a special crystal structure and is particularly suitable for serving as a carrier precursor of residual oil hydrodesulfurization catalysts.
According to one embodiment of the invention, step (1) comprises: the inorganic aluminum-containing compound solution, the phosphorus-containing compound, the grain growth regulator and acid or alkali are contacted for precipitation reaction, or the organic aluminum-containing compound, the phosphorus-containing compound and the grain growth regulator are subjected to hydrolysis reaction with water; controlling the pH of the precipitation reaction or the hydrolysis reaction to be 4-7.
According to a preferred embodiment of the present invention, the precipitation reaction or the hydrolysis reaction of step (1) is carried out in the presence of a grain growth regulator and a phosphorus-containing compound at a pH of 4 to 6.5. The precipitation reaction or the hydrolysis reaction is carried out at the preferable pH value, which is more beneficial to improving the desulfurization performance of the prepared carrier in the residual oil hydrogenation.
The conditions other than pH for the precipitation reaction and the hydrolysis reaction are not particularly limited. In the present invention, preferably, the temperature of the precipitation reaction and the hydrolysis reaction are each independently 30 to 90 ℃.
In the present invention, the conditions for the precipitation reaction are selected in a wide range, and preferably, the conditions for the precipitation reaction include: the reaction temperature is 40-90 ℃, and the reaction time is 10-60 minutes. Further preferably, the conditions of the precipitation reaction include: the reaction temperature is 45-80 ℃, and the reaction time is 10-30 minutes.
The conditions for the hydrolysis reaction are not particularly limited in the present invention, as long as water is brought into contact with the organic aluminum-containing compound to cause hydrolysis reaction to produce hydrated alumina. The water consumption in the hydrolysis reaction process is selected in a wider range, so long as the molar ratio of water to the organic aluminum-containing compound is greater than the stoichiometric ratio. Conditions under which hydrolysis specifically occurs are well known to those skilled in the art. Preferably, the conditions of the hydrolysis reaction include: the reaction temperature is 40-90 ℃, preferably 45-80 ℃, and the reaction time is 2-30 hours, preferably 2-20 hours.
In the present invention, the grain growth regulator is a substance capable of regulating the growth rate of grains on different crystal planes, preferably a substance capable of regulating the growth rate of grains on a 020 crystal plane and a 031 crystal plane. For example, it may be various substances capable of strongly adsorbing hydrated alumina, and preferably, the grain growth regulator is at least one of polyhydric sugar alcohol and its carboxylate and sulfate; further preferably, the grain growth regulator is at least one selected from the group consisting of sorbitol, glucose, gluconic acid, gluconate, ribitol, ribonic acid, ribonate and sulfate. The gluconate, the gluconate and the sulfate may each be a soluble salt thereof, for example, may be one or more of a potassium salt, a sodium salt and a lithium salt.
In the present invention, the manner of adding the grain growth regulator is not particularly limited, and the grain growth regulator may be added alone, or the grain growth regulator may be mixed with one or more of the raw materials in advance, and then the raw materials containing the grain growth regulator may be reacted.
The amount of the grain growth regulator used in the precipitation reaction is not particularly limited, and is preferably 1 to 10% by weight, more preferably 1.5 to 8.5% by weight, still more preferably 2 to 6% by weight, based on the weight of the inorganic aluminum-containing reactant.
Preferably, the grain growth regulator is used in the hydrolysis reaction in an amount of 1 to 10% by weight, preferably 1.5 to 8.5% by weight, and more preferably 2 to 6% by weight, based on the weight of the organic aluminum-containing compound, based on the alumina.
In the present invention, the amounts of the grain growth regulator are calculated based on the weight of the corresponding alumina in the organic aluminum-containing compound and the inorganic aluminum-containing compound, respectively, unless otherwise specified.
In the present invention, the manner of adding the phosphorus-containing compound is not particularly limited, and the phosphorus-containing compound (or the phosphorus-containing compound aqueous solution) may be added alone, or the phosphorus-containing compound (or the phosphorus-containing compound aqueous solution) may be mixed with one or more of the raw materials in advance, and then the raw materials containing the phosphorus-containing compound are reacted, so long as the precipitation reaction or the hydrolysis reaction is ensured to be carried out in the presence of the phosphorus-containing compound. The preparation method provided by the invention can ensure the regulation effect of the phosphorus-containing compound on the grain growth.
The phosphorus-containing compound of the present invention may be a water-soluble inorganic phosphorus-containing compound, and preferably, the phosphorus-containing compound is at least one selected from phosphoric acid, ammonium phosphate, ammonium hydrogen phosphate, diammonium hydrogen phosphate, sodium phosphate and potassium phosphate.
In order to better exert the effect of regulating the grain growth by the phosphorus-containing compound, the phosphorus-containing compound is preferably used in an amount such that the total dry weight of the phosphorus-containing pseudo-boehmite in the prepared phosphorus-containing pseudo-boehmite is taken as the reference, P 2 O 5 The content of (2) is 1 to 6% by weight, preferably 2 to 5% by weight.
It is noted that the crystal grain growth regulator and the phosphorus-containing compound are added during the precipitation reaction or the hydrolysis reaction, which is more favorable for regulating the growth speed of the crystal grain on the 020 crystal face and the 031 crystal face, so that h is more than or equal to 1.7 and less than or equal to 3, preferably 1.9 and less than or equal to 3, and more preferably 2.2 and less than or equal to 2.8. The grain growth regulator and the phosphorus-containing compound are added during the precipitation reaction or the hydrolysis reaction, so that the aging reaction carried out later is also carried out in the presence of the grain growth regulator and the phosphorus-containing compound. Preferably, no grain growth regulator or phosphorus-containing compound is additionally added during the aging process.
According to the method provided by the invention, the inorganic aluminium-containing compound is preferably an aluminium salt and/or an aluminate. Accordingly, the inorganic aluminum-containing compound solution may be various aluminum salt solutions and/or aluminate solutions, and the aluminum salt solution may be various aluminum salt solutions, for example, may be an aqueous solution of one or more of aluminum sulfate, aluminum chloride, and aluminum nitrate. Because of its low cost, aluminum sulfate solution and/or aluminum chloride solution are preferred. The aluminum salt may be used alone or in combination of two or more. The aluminate solution is any aluminate solution, such as sodium aluminate solution and/or potassium aluminate solution. Sodium aluminate solution is preferred because of its ease of availability and low cost. The aluminate solutions may also be used alone or in mixtures.
The concentration of the inorganic aluminum-containing compound solution is not particularly limited, and preferably the concentration of the inorganic aluminum-containing compound solution is 20 to 200 g/l in terms of aluminum oxide.
The acid may be various protonic acids or oxides acidic in an aqueous medium, for example, may be at least one of sulfuric acid, hydrochloric acid, nitric acid, carbonic acid, phosphoric acid, formic acid, acetic acid, citric acid, and oxalic acid, and preferably the protonic acid is at least one selected from nitric acid, sulfuric acid, and hydrochloric acid. The carbonic acid may be generated in situ by passing carbon dioxide into the aluminum salt solution and/or the aluminate solution. The acid may be introduced in the form of a solution, and the concentration of the acid solution is not particularly limited, preferably H + The concentration of (2) is 0.2-2 mol/L.
The alkali can be hydroxide or salt which is hydrolyzed in an aqueous medium to make the aqueous solution alkaline, preferably, the hydroxide is at least one selected from ammonia water, sodium hydroxide and potassium hydroxide; preferably, the salt is selected from at least one of sodium metaaluminate, potassium metaaluminate, ammonium bicarbonate, ammonium carbonate, sodium bicarbonate, sodium carbonate, potassium bicarbonate and potassium carbonate. The base may be introduced in the form of a solution, the concentration of the base solution Is not particularly limited, and preferably OH - The concentration of (2) is 0.2-4 mol/L. When sodium metaaluminate and/or potassium metaaluminate are used as the base, the amounts of the grain growth regulator and the phosphorus-containing compound are calculated, and the corresponding amounts of alumina in sodium metaaluminate and/or potassium metaaluminate are also considered.
According to the method provided by the invention, the organic aluminum-containing compound can be at least one of various aluminum alkoxides which can be subjected to hydrolysis reaction with water to generate hydrated alumina precipitate, and can be at least one of aluminum isopropoxide, aluminum isobutanol, aluminum triisopropoxide, aluminum trite-butoxide and aluminum isooctanolate.
Specifically, in order to regulate the pH of the hydrolysis reaction, an acid or a base may be introduced into the hydrolysis reaction, and the manner and kind of introduction of the acid or the base may be as described above, which will not be described herein.
Among them, the method of precipitating aluminum by controlling the pH with respect to the amount of alkali or acid in the reactant is well known to those skilled in the art, and will not be described herein.
The aging condition in the step (2) is selected in a wide range, so long as the aging condition is ensured to be performed under the condition that the pH is 7-10.5. Since the precipitation reaction or the hydrolysis reaction in step (1) is carried out at a pH of 4 to 7, it is preferable to introduce a base to adjust the pH of the aging reaction before aging is carried out. The manner and kind of introduction of the base may be as described above.
Preferably, the ageing of step (2) is carried out at a pH of 8-10.
The conditions of the aging other than pH in step (2) are selected in the present invention in a wide range, preferably the aging temperature is 50 to 95℃and preferably 55 to 90 ℃. The aging time is appropriately selected depending on the aging temperature, and preferably, the aging time is 0.5 to 8 hours, preferably 2 to 6 hours.
The invention also includes separating, washing and drying the aged product after the aging reaction. The separation according to the method provided by the present invention may be a method known in the art, such as filtration or centrifugation. The washing and drying method may be a method commonly used in the preparation of pseudo-boehmite, for example, the washing agent may be water and the drying may be at least one of drying, forced air drying, spray drying and flash drying. The drying temperature may be 100-350 ℃, preferably 120-300 ℃.
According to a preferred embodiment of the present invention, the preparation method comprises the steps of:
(1) Adding an inorganic aluminum-containing compound solution containing a phosphorus compound and a grain growth regulator and an alkali solution or an acid solution in parallel flow or intermittent flow into a reaction vessel for precipitation reaction to obtain phosphorus-containing hydrated alumina slurry; or adding a phosphorus-containing compound and a grain growth regulator into deionized water to carry out hydrolysis reaction with aluminum alkoxide to obtain phosphorus-containing hydrated alumina slurry, and carrying out precipitation reaction or hydrolysis reaction under the condition that the pH is 4-7, preferably 4-6.5 by using an acid solution or an alkali solution;
(2) Adding alkaline solution into the phosphorus-containing hydrated alumina slurry obtained in the step (1) to adjust the pH to 7-10.5, and aging for 0.5-8 hours at 50-95 ℃;
(3) Filtering and washing the product obtained in the step (2);
(4) And (3) drying the product obtained in the step (3) to obtain the phosphorus-containing pseudo-boehmite.
In a third aspect, the present invention provides the above-mentioned phosphorus-containing alumina, which is obtained by calcining phosphorus-containing pseudo-boehmite, wherein the phosphorus-containing pseudo-boehmite is the phosphorus-containing pseudo-boehmite according to the first aspect or the phosphorus-containing pseudo-boehmite obtained by the method according to the second aspect.
The conditions of the firing are not particularly limited in the present invention, and preferably the conditions of the firing include: the temperature is 450-700 ℃, preferably 500-650 ℃, and the time is 1-10 hours, preferably 2-6 hours.
In a fourth aspect, the present invention provides a phosphorus-containing alumina having an IR spectrum of (I) 3670 +I 3580 )/(I 3770 +I 3720 ) 1.9 to 2.8, preferably 2 to 2.7; wherein I is 3670 3670cm -1 Peak height, I 3580 3580cm -1 Peak height, I 3770 3770cm -1 Peak height, I 3720 3720cm -1 Peak height.
The phosphorus-containing alumina provided by the invention has specific surface hydroxyl distribution, and is used as a carrier for a residual oil hydrogenation catalyst, so that the catalyst has higher desulfurization activity.
The IR spectrum was measured by a Nicolet 870 Fourier infrared spectrometer from Nicolet corporation, USA. The method specifically comprises the following steps: the sample was pressed into a self-supporting sheet, placed in an infrared cell, and treated at 450℃for 3 hours under vacuum to determine the infrared spectrum of the sample. According to 3670cm on the spectrogram -1 Peak height at 3580cm -1 Peak height at 3770cm -1 Peak height at 3720cm -1 Calculation of the value of peak height (I 3670 +I 3580 )/(I 3770 +I 3720 ) Is a value of (2). Alumina carrier of the prior art (I) 3670 +I 3580 )/(I 3770 +I 3720 ) Typically lower than 1.8.
According to a fourth aspect of the present invention, there is provided a phosphorus-containing alumina obtained by calcining phosphorus-containing pseudo-boehmite, wherein the phosphorus-containing pseudo-boehmite is the phosphorus-containing pseudo-boehmite according to the first aspect or the phosphorus-containing pseudo-boehmite obtained by the method according to the second aspect.
According to the present invention, preferably, the phosphorus-containing alumina has a nitrogen adsorption pore volume of 1 to 1.6 ml/g, a BET nitrogen adsorption specific surface area of 270 to 380 square meters/g, and a pore diameter of 8 to 16 nm. The diameter of the holes refers to the diameter corresponding to the highest point of the hole distribution curve.
The phosphorus-containing alumina provided by the invention can be used as various adsorbents, catalyst carriers and matrixes of catalysts.
In a fifth aspect the present invention provides the use of the phosphorus containing alumina of the preceding third or fourth aspect in hydrodesulphurisation.
The present invention will be described in detail by examples. In the following examples, XRD was measured on a SIMENS D5005 type X-ray diffractometer, with CuK alpha radiation, 44 kilovolts, 40 milliamps, scanning at a rate of 2/min. According to the Scherrer formula: d=kλ/(bcosθ) (D is the grain size, λ is the diffraction wavelength of the target material, B is the half-width of the corrected diffraction peak, and 2θ is the position of the diffraction peak), the grain size of (020) is calculated as D (020) with the parameters of the 2θ as 10-15 ° peak, the grain size of (031) is calculated as D (031) with the parameters of the 2θ as 34-43 ° peak, and h=d (031)/D (020) is calculated.
The IR spectrum was measured by a Nicolet 870 Fourier infrared spectrometer from Nicolet corporation, USA. The method specifically comprises the following steps: the sample was pressed into a self-supporting sheet, placed in an infrared cell, and treated at 450℃for 3 hours under vacuum to determine the infrared spectrum of the sample. According to 3670cm on the spectrogram -1 Peak height at 3580cm -1 Peak height at 3770cm -1 Peak height at 3720cm -1 Calculation of the value of peak height (I 3670 +I 3580 )/(I 3770 +I 3720 ) Is a value of (2).
Example 1
This example is intended to illustrate the phosphorus-containing pseudo-boehmite and the phosphorus-containing alumina provided by the invention and the preparation method thereof.
In a 2L reaction tank, 5000 mL of aluminum sulfate solution with concentration of 60 g/L, 6.0 g of ribitol, 8.0mL of 85 wt% concentrated phosphoric acid and ammonia water solution with concentration of 6 wt% are added in parallel flow to carry out precipitation reaction, the reaction temperature is 50 ℃, the reaction time is 30 minutes, the flow rate of the ammonia water solution is controlled to enable the pH value of a reaction system to be 5.0, after the precipitation reaction is finished, a proper amount of ammonia water is added into slurry to enable the pH value of the slurry to be 8.7, the slurry is aged for 120 minutes at 70 ℃ and then filtered, a filter cake is pulped and washed by deionized water for 2 times, and the filter cake is dried for 24 hours at 120 ℃ to obtain hydrated aluminum oxide PA1, by XRD, PA1 has a pseudo-boehmite structure.
The h values calculated by XRD characterization to give PA1 are listed in Table 1. Relative crystallinity of PA1 and P 2 O 5 The content of (2) is also shown in Table 1.
The PA1 is roasted for 4 hours at 600 ℃ to obtain the phosphorus-containing aluminum oxide ZA1. The hydroxyl groups on the surface of the phosphorus-containing alumina were measured by infrared spectroscopy. (I) 3670 +I 3580 )/(I 3770 +I 3720 ) The values of (2) are listed in Table 2. Pore volume and specific surface area of phosphorus-containing alumina ZA1And the pore diameters are also shown in Table 2.
Comparative example 1
Pseudo-boehmite was prepared as in example 1, except that only 8.0mL of 85 wt.% phosphoric acid was added to the aluminum sulfate solution, without ribitol, to give hydrated alumina CPA1. CPA1 has pseudo-boehmite structure as characterized by XRD according to the method of example 1, and the h values calculated by XRD characterization are shown in Table 1 for CPA1, relative crystallinity and P 2 O 5 The content of (2) is also shown in Table 1. After roasting at 600 ℃ for 4 hours, measuring the hydroxyl groups on the surface of the phosphorus-containing alumina by using infrared spectrum, (I) 3670 +I 3580 )/(I 3770 +I 3720 ) The values of (2) are listed in Table 2. The pore volume, specific surface area and pore diameters of the phosphorus-containing alumina are also shown in Table 2.
Comparative example 2
Pseudo-boehmite was prepared in the same manner as in example 1 except that the flow rate of the aqueous ammonia solution was directly controlled to bring the pH of the reaction system to 8.7, and after the completion of the precipitation reaction, it was not necessary to add aqueous ammonia to the slurry to adjust the pH to obtain hydrated alumina CPA2. CPA2 has pseudo-boehmite structure as characterized by XRD according to the method of example 1, and the h values calculated by XRD characterization are shown in Table 1 for CPA2, relative crystallinity and P 2 O 5 The content of (2) is also shown in Table 1. After roasting at 600 ℃ for 4 hours, measuring the hydroxyl groups on the surface of the phosphorus-containing alumina by using infrared spectrum, (I) 3670 +I 3580 )/(I 3770 +I 3720 ) The values of (2) are listed in Table 2. The pore volume, specific surface area and pore diameters of the phosphorus-containing alumina are also shown in Table 2.
Comparative example 3
Pseudo-boehmite was prepared as in example 1 except that 6.0 g of ribitol alone was added to the aluminum sulfate solution without concentrated phosphoric acid to give hydrated alumina CPA3. The XRD characterization was performed as in example 1, CPA3 having pseudo-boehmite structure, and the h values calculated by XRD characterization are shown in Table 1, and the relative crystallinity is also shown in Table 1. After baking at 600 ℃ for 4 hours, the hydroxyl groups on the surface of the alumina are measured by infrared spectrum, (I) 3670 +I 3580 )/(I 3770 +I 3720 ) The values of (2) are listed in Table 2. The pore volume, specific surface area and pore diameters of the alumina are also shown in Table 2.
Example 2
This example is intended to illustrate the phosphorus-containing pseudo-boehmite and the phosphorus-containing alumina provided by the invention and the preparation method thereof.
In a 2L reactor, 4000 mL of an alumina solution containing 85 wt% concentrated phosphoric acid with a concentration of 45 g/L, 22.1mL of sorbitol and 4.52 g/L of aluminum trichloride and 1000 mL of a sodium metaaluminate solution containing 210 g of alumina/L and having a caustic coefficient of 1.58 are added in parallel to carry out precipitation reaction, the reaction temperature is 80 ℃, and the flow rate of reactants is regulated so that the neutralization pH value is 4.0, and the reaction residence time is 15 minutes; dilute ammonia water with the concentration of 5 weight percent is added into the obtained slurry to adjust the pH of the slurry to 9.0, the temperature is raised to 85 ℃, the aging is carried out for 3 hours, then a vacuum filter is used for filtering, and after the filtering is finished, 20 liters of deionized water (the temperature is 85 ℃) is added on a filter cake to wash the filter cake for about 30 minutes. And adding the qualified filter cake into 3 liters of deionized water, stirring to form slurry, pumping the slurry into a spray dryer for drying, controlling the outlet temperature of the spray dryer to be in the range of 100-110 ℃, and drying the material for about 2 minutes to obtain the hydrated alumina PA2. As characterized by XRD in accordance with the method of example 1, PA2 has a pseudo-boehmite structure, and the h values calculated by XRD characterization are shown in Table 1 for PA2, relative crystallinity and P 2 O 5 The content of (2) is also shown in Table 1. After roasting at 600 ℃ for 4 hours, measuring the hydroxyl groups on the surface of the phosphorus-containing alumina by using infrared spectrum, (I) 3670 +I 3580 )/(I 3770 +I 3720 ) The values of (2) are listed in Table 2. The pore volume, specific surface area and pore diameters of the phosphorus-containing alumina are also shown in Table 2.
Comparative example 4
Pseudo-boehmite was prepared as in example 2 except that the aluminum trichloride solution contained no sorbitol to give hydrated alumina CPA4. CPA4 has pseudo-boehmite structure as characterized by XRD according to the method of example 1, and the h values calculated by XRD characterization are shown in Table 1 for CPA4, relative crystallinity and P 2 O 5 The content of (2) is also shown in Table 1. After roasting at 600 ℃ for 4 hours, measuring the hydroxyl groups on the surface of the phosphorus-containing alumina by using infrared spectrum, (I) 3670 +I 3580 )/(I 3770 +I 3720 ) The values of (2) are listed in Table 2. The pore volume, specific surface area and pore diameters of the phosphorus-containing alumina are also shown in Table 2.
Comparative example 5
Pseudo-boehmite was prepared according to the method of example 2 except that the flow rate of the sodium metaaluminate solution was directly controlled to adjust the pH of the reaction system to 9.0, and that aqueous ammonia was not required to be added to the slurry to adjust the pH after the precipitation reaction was completed, to obtain alumina hydrate CPA5. CPA5 has pseudo-boehmite structure as characterized by XRD according to the method of example 1, and the h values calculated by XRD characterization are shown in Table 1 for CPA5, relative crystallinity and P 2 O 5 The content of (2) is also shown in Table 1. After roasting at 600 ℃ for 4 hours, measuring the hydroxyl groups on the surface of the phosphorus-containing alumina by using infrared spectrum, (I) 3670 +I 3580 )/(I 3770 +I 3720 ) The values of (2) are listed in Table 2. The pore volume, specific surface area and pore diameters of the phosphorus-containing alumina are also shown in Table 2.
Comparative example 6
Pseudo-boehmite was prepared as in example 2, except that the aluminum trichloride solution contained no concentrated phosphoric acid, yielding hydrated alumina CPA6. The XRD characterization was performed as in example 1, CPA6 having pseudo-boehmite structure, and the h values calculated by XRD characterization are shown in Table 1, and the relative crystallinity is also shown in Table 1. After baking at 600 ℃ for 4 hours, the hydroxyl groups on the surface of the alumina are measured by infrared spectrum, (I) 3670 +I 3580 )/(I 3770 +I 3720 ) The values of (2) are listed in Table 2. The pore volume, specific surface area and pore diameters of the alumina are also shown in Table 2.
Example 3
This example is intended to illustrate the phosphorus-containing pseudo-boehmite and the phosphorus-containing alumina provided by the invention and the preparation method thereof.
3000 ml of concentrated 3.5 g/l phosphoric acid with a concentration of 60 g/l alumina, a gluconic acid content of 4.5 g/l and 85% by weight are added in parallel to a 2 l reaction vesselThe precipitation reaction is carried out by using a solution of aluminum sulfate with a concentration of 200 g/L and a caustic coefficient of 1.58 and 1000 mL of sodium metaaluminate solution, the reaction temperature is 55 ℃, the flow rate of reactants is regulated to neutralize the pH value to 6.5, the reaction stays for 15 minutes, then a solution of sodium carbonate with a concentration of 100 g/L is added into the obtained slurry, the pH of the slurry is regulated to 9.5, the temperature is increased to 75 ℃, the aging is carried out for 5 hours, then the filtration is carried out by using a vacuum filter, and after the filtration is finished, 20L of deionized water (with a temperature of 85 ℃) is added to the filter cake to wash the filter cake for about 30 minutes. The filter cake was dried at 120℃for 24 hours to give hydrated alumina PA3. As characterized by XRD in accordance with the method of example 1, PA3 has a pseudo-boehmite structure, and the h values calculated by XRD characterization are shown in Table 1 for PA3, relative crystallinity and P 2 O 5 The content of (2) is also shown in Table 1. After roasting at 600 ℃ for 4 hours, measuring the hydroxyl groups on the surface of the phosphorus-containing alumina by using infrared spectrum, (I) 3670 +I 3580 )/(I 3770 +I 3720 ) The values of (2) are listed in Table 2. The pore volume, specific surface area and pore diameters of the phosphorus-containing alumina are also shown in Table 2.
Example 4
The procedure of example 3 was followed except that during the precipitation reaction, the reactant flow was adjusted so that the neutralization pH was 7. Hydrated alumina PA4 is obtained. As characterized by XRD in accordance with the procedure of example 1, PA4 has a pseudo-boehmite structure, and the h values calculated by XRD characterization are shown in Table 1 for PA4, relative crystallinity and P 2 O 5 The content of (2) is also shown in Table 1. After roasting at 600 ℃ for 4 hours, measuring the hydroxyl groups on the surface of the phosphorus-containing alumina by using infrared spectrum, (I) 3670 +I 3580 )/(I 3770 +I 3720 ) The values of (2) are listed in Table 2. The pore volume, specific surface area and pore diameters of the phosphorus-containing alumina are also shown in Table 2.
Comparative example 7
Pseudo-boehmite was prepared as in example 4 except that the aluminum sulfate solution contained no gluconic acid, resulting in hydrated alumina CPA7. CPA7 has pseudo-boehmite structure as characterized by XRD according to the method of example 1, and the h values calculated by XRD characterization are shown in Table 1 for CPA7, relative crystallinity and P 2 O 5 The content of (2) is also shown in Table 1. After roasting at 600 ℃ for 4 hours, measuring the hydroxyl groups on the surface of the phosphorus-containing alumina by using infrared spectrum, (I) 3670 +I 3580 )/(I 3770 +I 3720 ) The values of (2) are listed in Table 2. The pore volume, specific surface area and pore diameters of the phosphorus-containing alumina are also shown in Table 2.
Comparative example 8
Pseudo-boehmite was prepared according to the method of example 4, except that the flow rate of the sodium metaaluminate solution was directly controlled to make the pH of the reaction system 9.5, and that the pH was adjusted by adding sodium carbonate solution to the slurry after the precipitation reaction was completed, to obtain alumina hydrate CPA8. CPA8 has pseudo-boehmite structure as characterized by XRD according to the method of example 1, and the h values calculated by XRD characterization are shown in Table 1 for CPA8, relative crystallinity and P 2 O 5 The content of (2) is also shown in Table 1. After roasting at 600 ℃ for 4 hours, measuring the hydroxyl groups on the surface of the phosphorus-containing alumina by using infrared spectrum, (I) 3670 +I 3580 )/(I 3770 +I 3720 ) The values of (2) are listed in Table 2. The pore volume, specific surface area and pore diameters of the phosphorus-containing alumina are also shown in Table 2.
Comparative example 9
Pseudo-boehmite was prepared as in example 4, except that the aluminum sulfate solution contained no concentrated phosphoric acid, resulting in hydrated alumina CPA9. The XRD characterization was performed as in example 1, CPA9 having pseudo-boehmite structure, and the h values calculated by XRD characterization are shown in Table 1, and the relative crystallinity is also shown in Table 1. After baking at 600 ℃ for 4 hours, the hydroxyl groups on the surface of the alumina are measured by infrared spectrum, (I) 3670 +I 3580 )/(I 3770 +I 3720 ) The values of (2) are listed in Table 2. The pore volume, specific surface area and pore diameters of the alumina are also shown in Table 2.
Example 5
This example is intended to illustrate the phosphorus-containing pseudo-boehmite and the phosphorus-containing alumina provided by the invention and the preparation method thereof.
Into a 2 liter three-necked flask equipped with a stirring and reflux condenser, an isopropyl alcohol-water azeotrope (water content: 15% by weight) 1000 was introducedAnd (3) adding 4.6mL of 85% concentrated phosphoric acid and 15g of ribonucleotide, adding ammonia water to adjust the pH to 5.1, heating to 60 ℃, slowly dripping 500 g of melted aluminum isopropoxide into a flask through a separating funnel, reacting for 2 hours, adding ammonia water to adjust the pH to 8.5, refluxing for 20 hours, evaporating dehydrated isopropanol, aging at 80 ℃ for 6 hours, evaporating the water-containing isopropanol while aging, filtering the aged hydrated alumina, and drying at 120 ℃ for 24 hours to obtain the hydrated alumina PA5. As characterized by XRD in example 1, PA5 had pseudo-boehmite structure, and the h values calculated by XRD characterization are shown in Table 1 for PA5, relative crystallinity and P 2 O 5 The content of (2) is also shown in Table 1. After roasting at 600 ℃ for 4 hours, measuring the hydroxyl groups on the surface of the phosphorus-containing alumina by using infrared spectrum, (I) 3670 +I 3580 )/(I 3770 +I 3720 ) The values of (2) are listed in Table 2. The pore volume, specific surface area and pore diameters of the phosphorus-containing alumina are also shown in Table 2.
Comparative example 10
Pseudo-boehmite was prepared according to the method of example 5 except that no ribonic acid was added to the three-neck flask to give hydrated alumina CPA10. CPA10 has pseudo-boehmite structure as characterized by XRD according to the method of example 1, and the h values calculated by XRD characterization are shown in Table 1 for CPA10, relative crystallinity and P 2 O 5 The content of (2) is also shown in Table 1. After roasting at 600 ℃ for 4 hours, measuring the hydroxyl groups on the surface of the phosphorus-containing alumina by using infrared spectrum, (I) 3670 +I 3580 )/(I 3770 +I 3720 ) The values of (2) are listed in Table 2. The pore volume, specific surface area and pore diameters of the phosphorus-containing alumina are also shown in Table 2.
Comparative example 11
Pseudo-boehmite was prepared as in example 5 except that after adding the same amount of ribonucleotide, then ammonia was added to adjust the pH to 8.5, then heated to 60 ℃, and then 500 g of melted aluminum isopropoxide was slowly added dropwise to the flask through a separating funnel to obtain alumina hydrate CPA11. As characterized by XRD in accordance with the method of example 1, CPA11 has pseudo-boehmite structure, and the h values of CPA11 calculated by XRD characterization are shown in Table 1In (3) relative crystallinity and P 2 O 5 The content of (2) is also shown in Table 1. After roasting at 600 ℃ for 4 hours, measuring the hydroxyl groups on the surface of the phosphorus-containing alumina by using infrared spectrum, (I) 3670 +I 3580 )/(I 3770 +I 3720 ) The values of (2) are listed in Table 2. The pore volume, specific surface area and pore diameters of the phosphorus-containing alumina are also shown in Table 2.
Comparative example 12
Pseudo-boehmite was prepared as in example 5 except that concentrated phosphoric acid was not added to the three-neck flask to obtain hydrated alumina CPA12. The XRD characterization was performed as in example 1, CPA12 having pseudo-boehmite structure, and the h values calculated by XRD characterization are shown in Table 1, and the relative crystallinity is also shown in Table 1. After baking at 600 ℃ for 4 hours, the hydroxyl groups on the surface of the alumina are measured by infrared spectrum, (I) 3670 +I 3580 )/(I 3770 +I 3720 ) The values of (2) are listed in Table 2. The pore volume, specific surface area and pore diameters of the alumina are also shown in Table 2.
Example 6
This example is intended to illustrate the phosphorus-containing pseudo-boehmite and the phosphorus-containing alumina provided by the invention and the preparation method thereof.
Into a 2 liter three-neck flask with a stirring and reflux condenser, 1000 g of isopropyl alcohol-water azeotrope (water content: 15 wt%) was added, 7.0mL of 85% concentrated phosphoric acid, 12g of ribonic acid, and aqueous ammonia were added to adjust the pH to 6.2, heated to 60 ℃, 500 g of melted aluminum isopropoxide was slowly dropped into the flask through a separating funnel, reacted for 5 hours, and then, aqueous ammonia was added to adjust the pH to 8.5, after the reflux reaction for 20 hours, dehydrated isopropyl alcohol was distilled off, aged at 80℃for 6 hours, aqueous isopropyl alcohol was distilled off while aging, and after the aged hydrated alumina was filtered, dried at 120℃for 24 hours, to obtain hydrated alumina PA6. As characterized by XRD in accordance with the method of example 1, PA6 has a pseudo-boehmite structure, and the h values calculated by XRD characterization are shown in Table 1 for PA6, relative crystallinity and P 2 O 5 The content of (2) is also shown in Table 1. After roasting at 600 ℃ for 4 hours, measuring the hydroxyl groups on the surface of the phosphorus-containing alumina by using infrared spectrum, (I) 3670 +I 3580 )/(I 3770 +I 3720 ) The values of (2) are listed in Table 2. The pore volume, specific surface area and pore diameters of the phosphorus-containing alumina are also shown in Table 2.
Comparative example 13
The phosphorus-containing pseudo-boehmite is prepared according to the typical method in heavy oil hydrogenation catalyst carrier material research, and the concentration of 8.8mL of 85% concentrated phosphoric acid is 57 g.L -1 3000mL of aluminum sulfate solution with a concentration of 64 g.L -1 2500mL of sodium metaaluminate solution is subjected to precipitation reaction, the neutralization pH value is 8.0, the reaction time is 70min, then the aging is carried out, the aging temperature is 90 ℃, the aging pH value is 8.5, the filtering is carried out after the aging, the filter cake is pulped and washed by deionized water for 2 times, and the filter cake is dried at 120 ℃ for 24 hours to prepare the phosphorus-containing pseudo-boehmite CPA13. CPA13 has a pseudo-boehmite structure as characterized by XRD in accordance with the method of example 1, and the h values calculated by XRD characterization are shown in Table 1 for CPA13, relative crystallinity and P 2 O 5 The content of (2) is also shown in Table 1. After roasting at 600 ℃ for 4 hours, measuring the hydroxyl groups on the surface of the phosphorus-containing alumina by using infrared spectrum, (I) 3670 +I 3580 )/(I 3770 +I 3720 ) The values of (2) are listed in Table 2. The pore volume, specific surface area and pore diameters of the phosphorus-containing alumina are also shown in Table 2.
Comparative example 14
According to CN103721732A, a phosphorus-added modified pseudo-boehmite catalyst carrier material and a preparation method thereof are disclosed. Adding an aluminum sulfate solution with the alumina concentration of 50g/L and a sodium metaaluminate solution with the alumina concentration of 220g/L and the caustic ratio of 1.2 into a neutralization reaction kettle 1, controlling the pH value to be 7.0 and the temperature to be 55 ℃; the slurry of the neutralization reaction kettle 1 flows into the neutralization reaction kettle 2 through an overflow reaction pipe, meanwhile, sodium carbonate solution with the concentration of 150g/L is added into the neutralization reaction kettle 2, the pH is controlled to be 9.5, and the reaction temperature is controlled to be 70 ℃; the slurry in the neutralization reaction kettle 2 flows into an aging reaction kettle through an overflow reaction pipe, the temperature of the slurry in the aging reaction kettle is 95 ℃, and the aging is carried out for 2 hours; according to the mass of the alumina added in the reaction process of the neutralization reaction kettle 1, calculating the volume of a phosphoric acid solution with 100g/L phosphorus pentoxide concentration added into an aging reaction kettle, wherein the phosphorus pentoxide content of the added phosphoric acid is the content of the alumina4%; and (5) washing and drying after the aging is finished to obtain the phosphorus-containing pseudo-boehmite. The XRD characterization was performed as in example 1, CPA14 having pseudo-boehmite structure, and the h values calculated by XRD characterization are shown in Table 1, and the relative crystallinity is also shown in Table 1. After roasting at 600 ℃ for 4 hours, measuring the hydroxyl groups on the surface of the phosphorus-containing alumina by using infrared spectrum, (I) 3670 +I 3580 )/(I 3770 +I 3720 ) The values of (2) are listed in Table 2. The pore volume, specific surface area and pore diameters of the phosphorus-containing alumina are also shown in Table 2.
TABLE 1
Figure BDA0002472273140000211
Figure BDA0002472273140000221
TABLE 2
Figure BDA0002472273140000222
Figure BDA0002472273140000231
Note that: m represents (I) 3670 +I 3580 )/(I 3770 +I 3720 ) Values of (2)
As can be seen from the results of Table 1, the phosphorus-containing pseudo-boehmite prepared by the method provided by the invention has the characteristic that h is less than or equal to 1.7 and less than or equal to 3, preferably 2.2 and less than or equal to 2.8, and the h values of the pseudo-boehmite prepared by the prior art method and the method in the comparative example are all less than 1.7. As can be seen from the results in Table 2, the phosphorus-containing pseudo-boehmite prepared by the method of the invention has a characteristic (I) of hydroxyl groups in an IR characterization spectrum of alumina obtained by roasting the pseudo-boehmite at 600 DEG C 3670 +I 3580 )/(I 3770 +I 3720 ) 1.9-2.8, preferably 2-2.7, using prior art methods and the methods of the comparative examplesPseudo-boehmite prepared by the method is roasted at 600 ℃ to obtain the hydroxyl characteristic (I 3670 +I 3580 )/(I 3770 +I 3720 )<1.8。
Test example 1
300 g of pseudo-boehmite of the above examples 1 to 6 and comparative examples 1 to 14 was added with 3.5 g of nitric acid and a proper amount of deionized water, respectively, and mixed, kneaded, and kneaded for 30 minutes while adding water, and then extruded into a column having a diameter of 1.0 mm and a length of 3 to 5 mm, and dried and calcined at 600℃for 4 hours, to obtain an alumina carrier. The alumina carrier obtained was confirmed to be gamma-alumina from XRD. Then, the gamma-alumina carrier obtained above was saturated impregnated with a mixed solution of ammonium molybdate heptahydrate, aqueous ammonia and cobalt nitrate so as to contain 12.0 wt% of molybdenum oxide and 2.5 wt% of cobalt oxide, respectively, and dried and calcined at 450℃for 3 hours to prepare a hydrodesulfurization catalyst.
The hydrodesulfurization catalyst is presulfided, and presulfiding conditions include: the vulcanized oil adopts 5w percent of carbon disulfide/kerosene, and the liquid hourly space velocity of the vulcanized oil is 1.2h -1 The hydrogen partial pressure is 14.0MPa, the hydrogen oil volume ratio is 400, and the constant temperature sulfuration is carried out for 3 hours at 360 ℃; then, evaluation was performed in a 100 ml small fixed bed reactor (catalyst loading: 100 ml) using sauter Arabian light vacuum residuum (Ni+V 87.9. Mu.g/g, S3.18 wt%, MCR 12.4 wt%) as raw oil, each at a reaction temperature of 380℃and an LHSV of 0.50 hours, respectively -1 The desulfurization performance test is carried out under the conditions that the hydrogen partial pressure is 14.0 megapascal and the hydrogen oil volume ratio is 600, the sulfur content in residual oil after the desulfurization performance test is shown in table 3, and the lower the sulfur content is, the better the hydrodesulfurization performance of the catalyst is.
The sulfur content in the oil sample is determined by using an electric quantity method (the specific method is shown in RIPP62-90 of petrochemical analysis method).
TABLE 3 Table 3
Figure BDA0002472273140000241
Figure BDA0002472273140000251
As can be seen from Table 3, when the alumina prepared by roasting the phosphorus-containing pseudo-boehmite provided by the invention is used as a catalyst carrier, the catalyst has better desulfurization performance under the same other conditions.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.

Claims (17)

1. A method for preparing phosphorus-containing pseudo-boehmite, which comprises the following steps:
(1) The organic aluminum-containing compound is contacted with water to carry out hydrolysis reaction, so as to obtain hydrated alumina containing phosphorus;
(2) Aging the obtained hydrated alumina containing phosphorus at pH of 8-10;
the hydrolysis reaction in the step (1) is carried out in the presence of a grain growth regulator and a phosphorus-containing compound at a pH of 5 to 6.5; the grain growth regulator is a substance capable of regulating the growth speed of grains on different crystal faces;
the dosage of the phosphorus-containing compound is such that in the prepared phosphorus-containing pseudo-boehmite, P is based on the total dry basis of the phosphorus-containing pseudo-boehmite 2 O 5 The content of (2) is 1-6 wt%;
the substance capable of adjusting the growth rate of the crystal grains on different crystal planes is a substance capable of adjusting the growth rate of the crystal grains on a 020 crystal plane and a 031 crystal plane;
the substance capable of regulating the growth rate of the crystal grains on the 020 crystal face and the 031 crystal face is at least one of polyhydric sugar alcohol and carboxylate thereof;
in the hydrolysis reaction, the grain growth regulator is used in an amount of 1 to 10% by weight based on the weight of the organic aluminum-containing compound, based on the aluminum oxide.
2. The production method according to claim 1, wherein the temperature of the hydrolysis reaction is 30 to 90 ℃.
3. The production method according to claim 1 or 2, wherein the conditions of the hydrolysis reaction include: the reaction temperature is 40-90 ℃, and the reaction time is 2-30 hours.
4. A production method according to claim 3, wherein the conditions of the hydrolysis reaction include: the reaction temperature is 45-80 ℃ and the reaction time is 2-20 hours.
5. The production method according to claim 1 or 2, wherein the grain growth regulator is at least one selected from the group consisting of sorbitol, glucose, gluconic acid, gluconate, ribitol, ribonic acid and ribonate.
6. The production method according to claim 1 or 2, wherein the grain growth regulator is used in an amount of 1.5 to 8.5% by weight based on the weight of the organic aluminum-containing compound in the hydrolysis reaction, based on aluminum oxide.
7. The production method according to claim 6, wherein the grain growth regulator is used in an amount of 2 to 6% by weight based on the weight of the organic aluminum-containing compound in the hydrolysis reaction, based on the aluminum oxide.
8. The production method according to claim 1 or 2, wherein the phosphorus-containing compound is selected from at least one of phosphoric acid, ammonium phosphate, diammonium phosphate, sodium phosphate, and potassium phosphate.
9. The production method according to claim 1 or 2, wherein the phosphorus-containing compound is used in an amount such that, in the produced phosphorus-containing pseudo-boehmite, a dry mass of the phosphorus-containing pseudo-boehmite is usedBased on the total amount of radicals, P 2 O 5 The content of (2) is 2-5 wt%.
10. The production method according to claim 1 or 2, wherein the temperature of the aging is 50-95 ℃; the aging time is 0.5-8 hours.
11. The method of claim 10, wherein the aging temperature is 55-90 ℃; the aging time is 2-6 hours.
12. The preparation method according to claim 1 or 2, wherein,
the organic aluminum-containing compound is at least one of aluminum alkoxides which can generate hydrated aluminum oxide precipitate through hydrolysis reaction with water.
13. The production method according to claim 1 or 2, wherein the method produces a phosphorus-containing pseudo-boehmite, which compriseshMeets 1.9 to less than or equal tohNot more than 3, whereinhThe expression "D (031)/D (020)" is used to refer to the crystal grain size of the crystal plane represented by the 031 peak in the XRD spectrum of the pseudo-boehmite crystal grain, the D (020) is used to refer to the crystal grain size of the crystal plane represented by the 020 peak in the XRD spectrum of the pseudo-boehmite crystal grain, the 031 peak is the peak of 34-43 ° in the XRD spectrum, the 020 peak is the peak of 10-15 ° in the XRD spectrum, d=kλ/(bcosθ), K is the Scherrer constant, λ is the diffraction wavelength of the target material, B is the half-peak width of the diffraction peak, and 2θ is the position of the diffraction peak.
14. The method of claim 13, wherein the phosphorus-containing pseudo-boehmite ishMeets the requirement of 2.2 to less than or equal toh≤2.8。
15. The process according to claim 13, wherein Al is based on the total dry weight of phosphorus-containing pseudo-boehmite 2 O 3 The content of (C) is 94-99 wt%.
16. According to claim 15The preparation method comprises the following steps of taking the total dry basis of phosphorus-containing pseudo-boehmite as the reference, and Al 2 O 3 The content of (C) is 95-98 wt%.
17. The method of claim 13, wherein the relative crystallinity of the phosphorus-containing pseudo-boehmite is 45-77%.
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