CN103100433A - Preparation method of composite carrier material - Google Patents
Preparation method of composite carrier material Download PDFInfo
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- CN103100433A CN103100433A CN201110355794XA CN201110355794A CN103100433A CN 103100433 A CN103100433 A CN 103100433A CN 201110355794X A CN201110355794X A CN 201110355794XA CN 201110355794 A CN201110355794 A CN 201110355794A CN 103100433 A CN103100433 A CN 103100433A
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Abstract
The invention discloses a preparation method of a composite carrier material. The composite carrier material comprises a Y-type molecular sieve and an amorphous refractory inorganic oxide. The preparation method comprises that in NaY molecular sieve modification, amorphous refractory inorganic oxide slurry and a surfactant are used so that the molecular sieve and the amorphous refractory inorganic oxide are uniformly dispersed; molecular sieve agglomeration or channel blocking is avoided; a specific surface area and a pore volume of the composite carrier material are greatly improved; and catalyst performances are improved. The composite carrier material is especially suitable for being used as a carrier component of a hydrocracking catalyst.
Description
Technical field
The present invention relates to a kind of preparation method of composite carrier, a kind of preparation method who contains the catalyst carrier material of molecular sieve and amorphous refractory inorganic oxides specifically is especially for the preparation method of the catalyst carrier material that contains Y zeolite-amorphous refractory inorganic oxides of hydrocracking catalyst.
Background technology
In general, hydrocracking catalyst is a kind of catalyst that has simultaneously cracking function and hydrogenation-dehydrogenation functionality.The cracking function is to be provided by acid carrier, and the hydrogenation dehydrogenation functionality is to be provided by reactive metal, the acid carrier major part is take aluminium oxide or amorphous aluminum silicide as carrier, be equipped with a certain amount of molecular sieve, its basic preparation process is first aluminium oxide or silicon-containing alumina and molecular sieve and other auxiliary agent directly to be mixed, then carry out moulding, drying and roasting, final impregnating metal and activation.Amorphous aluminum silicide requires itself must have enough large specific area and pore volume as one of important component of catalyst carrier, with the carrying active metal component; Molecular sieve is mainly the acidic cleavage component, and for catalyst, cooperation both is most important, only has both coordinative roles, the catalytic action of competence exertion the best.In prior art, because molecular sieve adds by physical mixed, can not be in other carrier material of catalyst Uniform Dispersion, affect the reactivity worth of catalyst.
CN1110304A discloses the preparation method of the siliceous and phosphorus oxidation aluminium of a kind of macropore.In the preparation process of this aluminium oxide, silicon and phosphorus add with substep plastic method, can make like this silicon and phosphorus major part be dispersed in alumina surface, aluminium oxide aperture and pore volume are improved, but owing to having added more phosphorus, B acid amount greatly reduces to make the acid of alumina surface measure particularly, and acid strength obviously reduces, and its application is subject to certain restrictions.CN1184703A discloses a kind of preparation method of silicon-containing alumina.This silicon-containing alumina is a kind of alumina globule that silica is 5wt%～15wt% that contains, its preparation characteristic is that the silicon-containing alumina wet bulb after moulding carries out low temperature drying in containing the atmosphere of ammonia, the character of the alumina balls that obtain has obtained some improvement, but some defectives due to balling-up aspect self, make this forming process complicated, product yield is low, the shortcomings such as preparation cost height.EP0339640 discloses a kind of method for preparing titanium-contained aluminum oxide with coprecipitation, because coprecipitation itself exists the problem that body is detained mutually, causes titanium dioxide can not give full play to the facilitation of aluminium oxide.Require two or more species co-precipitation under certain condition due to co-precipitation, this condition to co-precipitation has proposed very harsh requirement, that is to say, even under certain conditions, two kinds of materials can precipitate simultaneously, but this condition may not be also all best to two kinds of materials, and the method has characteristics and the shortcoming of itself thus.CN1060977A discloses a kind of preparation method who contains the ultrastable of amorphous aluminum silicide, Alusil is introduced in the NaY zeolite, then obtained containing the USY zeolite of amorphous aluminum silicide through conventional ammonium ion exchange, hydrothermal calcine process.The main deficiency of the method is: the part amorphous aluminum silicide is easy to enter in molecular sieve pore passage, not only stop up molecular sieve pore passage, pore volume and the specific area of molecular sieve have been reduced, but also covered the part acid site, affected the catalytic performance of molecular sieve, also affect simultaneously the modification process of molecular sieve, the catalytic performance of molecular sieve and amorphous aluminum silicide can not be played one's part to the full.
CN200610134151.1 discloses a kind of preparation method who contains the carrier material of molecular sieve and amorphous aluminum silicide.Molecular sieve in carrier is introduced in amorphous aluminum silicide plastic process.In the method, reuniting can appear in silica-alumina supports in molecular sieve, and perhaps molecular sieve and amorphous aluminum silicide enter mutually the other side's duct, have blocked the part duct and have covered a part of acid site, makes carrier specific area, pore volume and acidity increase limited.
Summary of the invention
For the deficiencies in the prior art part, the invention provides a kind of preparation method with bigger serface, large pore volume, acid suitable composite carrier.The method makes the more even of molecular sieve and the dispersion of amorphous refractory inorganic oxides, having overcome molecular sieve easily occurs reuniting, perhaps molecular sieve and amorphous refractory inorganic oxides enter mutually the other side's duct and block the part duct, and specific area, pore volume and the acidity of carrier are greatly improved.
The preparation method of composite carrier of the present invention, described carrier material comprises Y zeolite and amorphous refractory inorganic oxides, and wherein the content of amorphous refractory inorganic oxides is 40wt%～90wt%, and preparation process is as follows:
(l) needed amorphous refractory inorganic oxides is added the water making beating;
(2) in the molecular sieve modified process of NaY, introduce slurries and the surfactant of step (1) gained, take the weight of final carrier material as benchmark, the addition of surfactant is 2wt%～20wt%;
(3) material of step (2) gained is comprised the treatment step of filtration, washing, drying, obtain containing the composite carrier of Y zeolite and amorphous refractory inorganic oxides.
In step of the present invention (l), amorphous refractory inorganic oxides can be one or more in aluminium oxide, silica, magnesia, titanium oxide, zirconia, is preferably silica-alumina (being amorphous aluminum silicide).Amorphous aluminum silicide used can be by the preparation of coprecipitation or grafting copolymerization process, press in document conventional method and prepares and get final product.SiO in the amorphous aluminum silicide of gained
2Weight content be 20% ~ 50%, be preferably 30% ~ 45%.In the slurries of step (1) gained, the content of amorphous refractory inorganic oxides is 5wt%～40wt%.
The molecular sieve modified process of NaY of the present invention can be carried out modification according to specific needs, comprises one or more in ion-exchange, hydrothermal treatment consists, acid treatment etc.The NaY molecular sieve is after modification, and resulting Y zeolite type can be the Y zeolite (SSY) of deep sealumination modified Y type molecular sieve (DAY), super-stable Y molecular sieves (USY), silicon replacement or the Y zeolite (US-SSY) that super steady silicon replaces.
The surfactant of step of the present invention (2) is preferably nonionic surface active agent, as: one or more in polyglycol ether, APES, AEO, polyoxyethylene carboxylate, polyoxyethylene amine, polyoxyethylate amide, fatty glyceride etc.Described surfactant preferably adds with the form of the aqueous solution, is about to surfactant and is added to the water the aqueous solution that formation contains surfactant.
The material of the gained of step (2) described in step of the present invention (3) comprises process and the condition that filtration, washing, drying and other steps are well known to the skilled person, the processing procedure such as can also comprise pulverizing, sieve.Described drying generally adopts oven drying, and drying condition is as follows: drying is 6～10 hours under 80～120 ℃.
In the composite carrier of the inventive method preparation, the Y zeolite weight content is 10wt%～60wt%, and the content of amorphous refractory inorganic oxides is 40wt%～90wt%, and this carrier material has following character: specific area is 400m
2/ g～1000m
2/ g, pore volume are 0.6cm
3/ g～2.0cm
3/ g, infrared acidity is 0.3～1.0mmol/g.
The composite carrier of the inventive method preparation is suitable for the carrier component as Cracking catalyst, the suitable especially carrier component as hydrocracking catalyst.
the present invention contains in the preparation process of composite carrier of molecular sieve and amorphous refractory inorganic oxides, amorphous refractory inorganic oxides is introduced in the Y zeolite modifying process, add simultaneously surfactant, not only can make Y zeolite and amorphous refractory inorganic oxides Uniform Dispersion, both form good coordinative role in catalytic process, the serviceability that improves catalyst had good facilitation, and surfactant has the characteristics of dispersion, the surfactant molecule structure has amphipathic: an end is hydrophilic radical, the other end is the hydrophobic group, molecular sieve has hydrophobicity, amorphous refractory inorganic oxides has hydrophily, amorphous like this refractory inorganic oxides, surfactant and molecular sieve Uniform Dispersion, ordered arrangement, avoided Y zeolite can occur reuniting in carrier, perhaps Y zeolite and amorphous refractory inorganic oxides enter mutually the other side's duct, block part duct and cover part acid centre, make the specific area of carrier material, pore volume and acidity are greatly improved.
The specific embodiment
The specific area of product of the present invention and pore volume are to adopt ASAP2405, and the low temperature liquid nitrogen absorption method records.Meleic acid amount, B acid and L acid are to adopt infra-red sepectrometry to record, and the adsorbent that uses is pyridine.Wt% is mass fraction.
Further illustrate technical scheme of the present invention below in conjunction with specific embodiment.Embodiment 1
Composite carrier B according to method preparation provided by the invention.
With 1000g amorphous aluminum silicide (dioxide-containing silica is 30wt%), add in 2 liters of distilled water, stirring to pulp forms slurries (a), and the 100g polyoxyethylate amide is dissolved in 1L water, forms solution (b), gets the 250 industrial NaY zeolite of gram (SiO
2/ A1
2O
3=5.0(mol ratio), lattice constant is 2.463nm, Na
2O content is 9wt%), with the NH of 2500ml 10%
4NO
3The aqueous solution exchanges 1 hour at 90 ℃ of temperature, and then is 2 oxalic acid and NH with 2500ml pH value
4NO
3Mixed liquor carries out secondary exchange, adds simultaneously slurries (a) and solution (b) solution, carries out afterwards for the first time hydrothermal treatment consists 2 hours under 0.098 MPa and 550 ℃ of conditions, then uses 10% NH
4NO
3The aqueous solution exchanges to Na
2After O＜0.15wt%, carrying out for the second time hydrothermal treatment consists 2 hours under 0.12MPa and 650 ℃ of conditions, is then the HNO of 0.3mol/L with concentration
3Aqueous solution exchange after filtration, washing, then 120 ℃ of dryings 4 hours, makes composite carrier A.
Embodiment 2
Composite carrier B according to method preparation provided by the invention.
With 1000g amorphous aluminum silicide (dioxide-containing silica is 30wt%), add in 2 liters of distilled water, stirring to pulp forms slurries (a), and the 120g polyglycol ether is dissolved in 1L water, forms solution (b), gets the 250 industrial NaY zeolite of gram (SiO
2/ A1
2O
3=5.0(mol ratio), lattice constant is 2.463nm, Na
2O content is 9wt%), with the NH of 2500ml 10%
4NO
3The aqueous solution exchanges 1 hour at 90 ℃ of temperature, and then is 2 oxalic acid and NH with 2500ml pH value
4NO
3Mixed liquor carries out secondary exchange, carries out afterwards for the first time hydrothermal treatment consists 2 hours under 0.098 MPa and 550 ℃ of conditions, then is being the NH of 10wt% with concentration
4NO
3The aqueous solution exchanges to Na
2O＜0.15wt% adds (a) and (b) after solution simultaneously, carries out for the second time hydrothermal treatment consists 2 hours under 0.12MPa and 650 ℃ of conditions, is then 0.3 mol/L HNO with concentration
3Aqueous solution exchange after filtration, washing, 120 ℃ of dryings 4 hours, makes composite carrier B.
Embodiment 3
Composite carrier C according to method preparation provided by the invention.
With 1000g amorphous aluminum silicide (dioxide-containing silica is 20wt%), add in 2 liters of distilled water, stirring to pulp forms slurries (a), and 150g polyoxyethylene amine solvent forms solution (b) in 1L water, get the 250 industrial NaY zeolite of gram (SiO
2/ A1
2O
3=5.0(mol ratio), lattice constant is 2.463nm, Na
2O content is 9wt%), with the NH of 2500ml 10%
4NO
3The aqueous solution exchanges 1 hour at 90 ℃ of temperature, and then is 2 oxalic acid and NH with 2500ml pH value
4NO
3Mixed liquor carries out secondary exchange, adds simultaneously slurries (a) and solution (b) solution, carries out afterwards for the first time hydrothermal treatment consists 2 hours under 0.098 MPa and 550 ℃ of conditions, then uses 10% NH
4NO
3The aqueous solution exchanges to Na
2After O＜0.15wt%, carrying out for the second time hydrothermal treatment consists 2 hours under 0.12MPa and 650 ℃ of conditions, is then the HNO of 0.3mol/L with concentration
3Aqueous solution exchange after filtration, washing, then 120 ℃ of dryings 4 hours, makes composite carrier C.
Comparative example 1
The reference carrier material C that the method that provides according to CN901108741.6 (CN1060977A) prepares
A
L. get the 250 industrial NaY zeolite of gram (SiO
2/ A1
2O
3=5.0(mol ratio), lattice constant is 2.463nm, Na
2O content is 9wt%), be dispersed in the mother liquor (SiO that 14000g synthesizes the NaY gained
2Content 5wt%) in, add while stirring AlCl under room temperature
3(A1
2O
3Content 3.0 wt%) solution 10000g, slurry pH value is 8.2, filters.
2. the 1st step gained filter cake mixes with appropriate ammonium sulfate, and make zeolite: ammonium sulfate: water=1: 1: 40 (weight ratio), slurries are warming up to 90 ℃, carry out ion-exchange reactions 1.0 hours, and then are 2 oxalic acid and NH with 2500ml pH value
4NO
3Mixed liquor carried out hydrothermal treatment consists 2 hours after carrying out the secondary exchange under 0.098MPa and 550 ℃ of conditions, make reference carrier material C
A
Comparative example 2
1. get the 250 industrial NaY zeolite of gram (SiO
2/ A1
2O
3=5.0(mol ratio), lattice constant is 2.463nm, Na
2O content is 9wt%), be the NH of 10wt% with 2500ml concentration
4NO
3The aqueous solution exchanges 1 hour at 90 ℃ of temperature, and then is 2 oxalic acid and NH with 2500ml pH value
4NO
3Mixed liquor carries out secondary exchange, carries out afterwards for the first time hydrothermal treatment consists 2 hours under 0.098 MPa and 550 ℃ of conditions, then with 10% NH
4NO
3The aqueous solution exchanges to Na
2After O＜0.15wt%, carrying out for the second time hydrothermal treatment consists 2 hours under 0.12MPa and 650 ℃ of conditions, is then 0.3 mol/L HNO with concentration
3Aqueous solution exchange through washing, 120 ℃ of dryings 4 hours, makes Modified Zeolite Y (press CN02144945.7 prepares).
2. said method is made 15g modified Y molecular sieve, 75g amorphous aluminum silicide (dioxide-containing silica is 30wt%), 10g SB aluminium oxide and rare nitric acid kneading roll, but make the paste of extrusion, extruded moulding, 110 ℃ of dryings 6 hours make reference composite carrier C
B
Comparative example 3
The reference carrier material C that the method that provides according to CN200610134151.1 prepares
C
With the modified Y molecular sieve of 150g comparative example 2 gained, add in 2 liters of distilled water, stirring to pulp forms slurries (a), and 4000g solid sulphuric acid aluminium is joined in 7.5 liters of distilled water, heats simultaneously and is stirred to dissolving, obtains aluminum sulfate solution (b), A1
2O
3Concentration is 4g/100ml approximately.Add appropriate distilled water diluting into about 10% weak aqua ammonia (c) concentrated ammonia liquor.10 liters of distilled water are joined in 4.8L concentrated sodium silicate (technical grade, modulus are 3.0), obtain rare water glass solution (d).Get the steel retort of one 15 liters, after adding 2 liters of distilled water in tank and being heated with stirring to 70 ℃, open simultaneously the valve of the container that has respectively aluminum sulfate and ammoniacal liquor, and slowly add (a) in retort, by the flow of preparation 750g sial product setting value (b) so that the neutralization reaction time at one hour, adjust simultaneously the speed that adds of (a), guarantee to add simultaneously at (a) with (b), and the flow of adjusting rapidly (c) makes the pH value of system remain on 7～8, and the temperature of the hierarchy of control is 65 ℃ of left and right.After reacting aluminum sulfate is completed, stop adding ammoniacal liquor, after the alumina sol of generation is stablized 20 minutes, by finally containing SiO
2Amount begins to add 3.3 liters of meterings (d), adds in 10 minutes, and the ageing process of beginning system keeps the pH value 8.0,60～65 ℃ of temperature.After aging 50 minutes, filter colloidal solution and obtain wet cake, with the making beating of filter cake adding distil water again washing, refilter and obtain filter cake (e).After under 110 ℃ dry 8 hours, composite carrier C pulverizes, sieves and to get with (e)
C
The physico-chemical property of table 1 complex carrier
| Numbering | A | B | C | C A | C B | C C |
| Specific area, m 2/g | 485 | 482 | 501 | 289 | 380 | 340 |
| Pore volume, ml/g | 0.71 | 0.68 | 0.76 | 0.45 | 0.63 | 0.51 |
| The meleic acid amount, mmol/g | 0.449 | 0.457 | 0.431 | 0.565 | 0.405 | 0.392 |
Claims (10)
1. the preparation method of a composite carrier, described carrier material comprises Y zeolite and amorphous refractory inorganic oxides, and wherein the content of amorphous refractory inorganic oxides is 40wt%～90wt%, and preparation process is as follows:
(l) needed amorphous refractory inorganic oxides is added the water making beating;
(2) in the molecular sieve modified process of NaY, introduce slurries and the surfactant of step (1) gained, take the weight of final carrier material as benchmark, the addition of surfactant is 2wt%～20wt%;
(3) material of step (2) gained is comprised the treatment step of filtration, washing, drying, obtain containing the composite carrier of Y zeolite and amorphous refractory inorganic oxides.
2. in accordance with the method for claim 1, it is characterized in that in step (2), described surfactant adds with the form of the aqueous solution.
3. in accordance with the method for claim 1, it is characterized in that amorphous refractory inorganic oxides in step (l) is one or more in aluminium oxide, silica, magnesia, titanium oxide, zirconia.
4. in accordance with the method for claim 1, it is characterized in that in step (l), amorphous refractory inorganic oxides is amorphous aluminum silicide, wherein SiO
2Weight content be 20% ~ 50%.
5. in accordance with the method for claim 1, it is characterized in that in the slurries of step (1) gained, the content of amorphous refractory inorganic oxides is 5wt%～40wt %.
6. in accordance with the method for claim 1, it is characterized in that the molecular sieve modified process of described NaY comprises one or more in ion-exchange, hydrothermal treatment consists, acid treatment.
7. in accordance with the method for claim 1, it is characterized in that described NaY molecular sieve after modification, resulting Y zeolite is the Y zeolite of deep sealumination modified Y type molecular sieve, super-stable Y molecular sieves, silicon replacement or the Y zeolite that super steady silicon replaces.
8. the surfactant that in accordance with the method for claim 1, it is characterized in that step (2) is nonionic surface active agent.
9. the surfactant that in accordance with the method for claim 1, it is characterized in that step (2) is one or more in polyglycol ether, APES, AEO, polyoxyethylene carboxylate, polyoxyethylene amine, polyoxyethylate amide, fatty glyceride.
10. in accordance with the method for claim 1, it is characterized in that the described drying of step (3) is under 80～120 ℃ dry 6～10 hours.
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| CN103100433B CN103100433B (en) | 2015-05-13 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106607071A (en) * | 2015-10-26 | 2017-05-03 | 中国石油化工股份有限公司 | Preparing method for high-cracking-activity Y-shaped molecular sieve |
| CN106669771A (en) * | 2015-11-09 | 2017-05-17 | 中国石油化工股份有限公司 | Compound containing nano NaY molecular sieve and preparation method thereof |
| CN106669772A (en) * | 2015-11-09 | 2017-05-17 | 中国石油化工股份有限公司 | Compound and preparation method thereof |
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| CN101172259A (en) * | 2006-11-01 | 2008-05-07 | 中国石油化工股份有限公司 | Method for preparing carrier material |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106607071A (en) * | 2015-10-26 | 2017-05-03 | 中国石油化工股份有限公司 | Preparing method for high-cracking-activity Y-shaped molecular sieve |
| CN106607071B (en) * | 2015-10-26 | 2019-03-22 | 中国石油化工股份有限公司 | A kind of preparation method of high cracking activity Y type molecular sieve |
| CN106669771A (en) * | 2015-11-09 | 2017-05-17 | 中国石油化工股份有限公司 | Compound containing nano NaY molecular sieve and preparation method thereof |
| CN106669772A (en) * | 2015-11-09 | 2017-05-17 | 中国石油化工股份有限公司 | Compound and preparation method thereof |
| CN106669772B (en) * | 2015-11-09 | 2019-05-21 | 中国石油化工股份有限公司 | A kind of compound and preparation method thereof |
| CN106669771B (en) * | 2015-11-09 | 2019-06-11 | 中国石油化工股份有限公司 | A kind of compound and preparation method thereof containing nano NaY molecular sieve |
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