CN102311129A - Method for preparing high-silicon Y-type molecular sieves - Google Patents

Method for preparing high-silicon Y-type molecular sieves Download PDF

Info

Publication number
CN102311129A
CN102311129A CN2010102223881A CN201010222388A CN102311129A CN 102311129 A CN102311129 A CN 102311129A CN 2010102223881 A CN2010102223881 A CN 2010102223881A CN 201010222388 A CN201010222388 A CN 201010222388A CN 102311129 A CN102311129 A CN 102311129A
Authority
CN
China
Prior art keywords
molecular sieve
type molecular
ammonium salt
silicofluoric acid
raw material
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN2010102223881A
Other languages
Chinese (zh)
Other versions
CN102311129B (en
Inventor
汤涛
王敏
凌凤香
王丽君
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
Original Assignee
China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by China Petroleum and Chemical Corp, Sinopec Fushun Research Institute of Petroleum and Petrochemicals filed Critical China Petroleum and Chemical Corp
Priority to CN 201010222388 priority Critical patent/CN102311129B/en
Publication of CN102311129A publication Critical patent/CN102311129A/en
Application granted granted Critical
Publication of CN102311129B publication Critical patent/CN102311129B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Landscapes

  • Catalysts (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)

Abstract

The invention relates to a method for preparing high-silicon Y-type molecular sieves, which comprises the steps of: using NaY type molecular sieves as raw materials; preparing the NaY type molecular sieves into serous liquid; firstly carrying out fluosilicic acid treatment; directly adding ammonium salt after the fluosilicic acid treatment; and obtaining modified high-silicon Y-type molecular sieves through separation after ammonium salt treatment. Compared with the prior art, the NaY molecular sieve treatment process of the method has the advantages that the process is simple, the energy consumption is low, the modified effect is good, the consumption of modified materials is low, and the like. Modified high-silicon Y-type molecular sieves meeting various property requirements can be prepared.

Description

A kind of preparation method of high-Si Y-type molecular sieve
Technical field
The present invention relates to a kind of preparation method of Modified Zeolite Y, particularly the preparation method of modification high-Si Y-type molecular sieve.
Background technology
Y zeolite has been widely used in preparation catalytic cracking, hydrogen cracking in industry, different acid catalyzed reaction catalyzer or support of the catalyst such as isomerizing and alkylation.Positively charged ion outside the Y zeolite of Direct Water thermal synthesis, skeleton is Na normally +, and the NaY molecular sieve does not possess the acid catalysis activity, therefore when being used to prepare the acid catalyzed reaction catalyzer, must remove most of Na +Requiring to take off the sodium degree when not really high, can adopt ion exchange technique, through once or IX several times realize.But requiring to take off the sodium degree when higher; Owing to only adopt ion exchange technique just can reach requirement through the exchange of tens times, tens times and even secondary ion up to a hundred; Such process does not have the economy of industrial application, therefore, all is to adopt energy-intensive Na usually 2O roasting and ion exchange phase bonded method, the patented technology of relevant this respect is a lot, and is typical in US3293192, US3402996, US3781199 and US4036739 etc.
Generally speaking, through taking off Na +Replace Na in the Y zeolite of handling +Be H +Or NH 4 +Positively charged ion.And H +Or NH 4 +Positively charged ion greatly can be from normal associating AlO with it 4 -Slough in the tetrahedron, on molecular sieve structure, produce electrovalent imbalance, this will cause its structural rearrangement, to recover the electricity price balance.Some researchs show, in the total skeleton tetrahedron of molecular sieve, contain the AlO greater than 40% 4 -During tetrahedron, required structural rearrangement just can not adapt to, thereby crystalline structure will be damaged.Therefore in order to guarantee the stability of Y zeolite crystalline structure, particularly at high temperature thermostability must remove the aluminium atom in the part crystal.The y-type zeolite dealuminzation, existing method mainly contains: 1) complexing dealuminzation method (like US 3442795, US3640681, US4093560): 2) high-temperature water heat treating process (like US3493519, US3506400, US3513108 etc.); 3) SiCl. gas-phase silicon method of substitution; With 4) (the NH relevant with the present invention 4) 2SiF 6Liquid-phase silicone method of substitution (like US4503023).(NH wherein 4) 2SiF 6The liquid-phase silicone method of substitution is that part is taken off the NH behind the sodium 4The NaY molecular sieve is processed slurries, makes reaction system keep certain acidity with acid or buffer reagent, adds (NH 4) 2SiF 6Carry out the silicon substitution reaction, realize removing framework of molecular sieve aluminium.
Can find out from above-mentioned prior art, prepare the low sodium Y zeolite of high silicon.Must be through above-mentioned sodium and two processes of dealuminzation of taking off, the preparation process is complicacy comparatively, particularly takes off the sodium process.If require sodium content to reduce to very low degree, also need adopt the calcination steps of highly energy-consuming.
CN90102645.X provides a kind of preparation method of low-Na and high-Si Y-type molecular sieve, simplifies preparation process, saves the Na of highly energy-consuming 2The O roasting, but raw material needs Na 2The product that O content is relatively low, as require Na 2O content is lower than 3%, and the Na of the NaY type molecular sieve of Direct Water thermal synthesis 2O content can reach about 10%.Therefore this method raw material receives certain restriction, for obtaining certain SiO 2/ Al 2O 3The product of molecular ratio requires the sodium content of raw material can not be too high, generally need carry out the ammonium salt exchange earlier and just can achieve the goal.
Summary of the invention
To the deficiency of prior art, the present invention provides a kind of preparation method of low-Na and high-Si Y-type molecular sieve, simplifies preparation process, saves the Na of highly energy-consuming 2The O roasting, and can be the feedstock production low-Na and high-Si Y-type molecular sieve with NaY directly, do not limit the sodium content of raw material.
The preparation method of the low sodium Y zeolite of the high silicon of the present invention comprises following content: with NaY type molecular sieve is raw material; NaY type molecular sieve is processed slurries; At first carrying out silicofluoric acid handles; The silicofluoric acid consumption is every 100gNaY type molecular sieve raw material more than 0.05 mole, is generally 0.05～0.5 mole, is preferably 0.08～0.4 mole; Silicofluoric acid is handled the back and is directly added ammonium salt, and the ammonium salt consumption adds 5g at least, preferably 10～50g by every 100g Y zeolite raw material; Ammonium salt separates after handling, and obtains the modification high-Si Y-type molecular sieve.
In the inventive method, the concentration that the molecular sieve raw material is processed slurries is generally, and every 100mL slurries contain 5～30g raw material Y zeolite, and preferably every 100mL slurries contain 10～25g raw material Y zeolite.The temperature of molecular sieve modified treating processes is generally 50～120 ℃, is preferably 70～100 ℃.
Silicofluoric acid generally adds with the solution form; Strength of solution is generally 0.01～5mol/L; Be preferably 0.1～2mol/L; Silicofluoric acid adds speed and per hour adds 0.02～0.1 mole of silicofluoric acid by every 100g Y zeolite, under agitation keeps 0.1～24 hour after adding silicofluoric acid, preferably keeps 0.5～5 hour.
Silicofluoric acid is handled the back material and need do not separated, and directly adds ammonium salt, and ammonium salt can adopt solution or solid form to add.Under agitation kept 0.1～24 hour after adding ammonium salt, preferably kept 0.5～5 hour.Ammonium salt is generally an ammonium nitrate, ammonium acetate, volatile salt, bicarbonate of ammonia, ammonium sulfate, ammonium chloride etc., is preferably an ammonium nitrate.
After ammonium salt is handled, material is separated, modified Y molecular sieve carries out processing such as drying and obtains the high silicon Y molecular sieve of final modification product.
When preparing low-Na and high-Si Y-type molecular sieve with method of the present invention, must be according to the sodium content and the SiO of product Y zeolite requirement 2/ Al 2O 3Molecule is recently selected the ratio of suitable an ammonium nitrate and silicofluoric acid.
The NaY that the inventive method is used is industrial synthetic product, does not generally need modification to handle its SiO 2/ Al 2O 3Molecular ratio between 3.5～7.0, preferably 4.5～7.0, Na 2O content is generally about 10%, changes to some extent by the different above-mentioned character of synthesis condition.
The preparation method of the low sodium Y zeolite of high silicon of the present invention is a raw material with direct synthetic NaY type molecular sieve, under conditions suitable, carries out silicofluoric acid earlier and handles, and adds ammonium salt then and handles.NaY type molecular sieve and silicofluoric acid reaction, properties-correcting agent (silicofluoric acid) utilization ratio is high.Well-known fluosilicic acid root combines meeting and produces precipitation with sodium; Owing to when fluosilicic acid is handled, do not have a large amount of ion-exchange and take place, the sodium of the big branch of NaY type molecular sieve is in molecular sieve in the inventive method; Less in the environmental system; Therefore the modifier that precipitates and consume is less, has improved its effective rate of utilization, reduces the loss.After silicofluoric acid is handled, add ammonium salt, the reaction of carrying out is mainly the ammonium exchange, has the modified-reaction of silicofluoric acid simultaneously.The NaY molecular sieve treating processes that the inventive method adopts has advantages such as process is simple, energy consumption is low, modified effect is good, the modification supplies consumption is low, can prepare the high silicon Y molecular sieve of modification that various character require.
Embodiment
The high silicon Y molecular sieve of the inventive method modification prepares process and is: raw material NaY type molecular sieve is processed slurries with zero(ppm) water or deionized water; Slurries are after adding the silicofluoric acid certain hour under the stirring that heats up; Add aqueous ammonium nitrate solution or solid; Make the Y zeolite raw material carry out modified-reaction, remove the Na in the molecular sieve +With the part framework aluminum.
A kind of concrete treating processes of the inventive method is following:
1. the molecular sieve raw material is processed certain density slurries, and every 100mL slurries contain 5～30g raw material Y zeolite, and preferably every 100mL slurries contain 10～25g raw material Y zeolite;
2. reaction mixture temperature maintains 50～120 ℃ in the reaction process, preferably 70～100 ℃;
3. the adding silicofluoric acid is an example with 0.1mol/L solution, generally is added to few 500mL, preferably 800～5000mL by every 100gY type molecular sieve raw material;
4. the adding speed of control silicofluoric acid is example with 0.1mol/L solution, general per hour pressing, and every 100gY type molecular sieve raw material adds in the 1500mL, preferably 200～1000mL;
5. keep the suitable reaction times, promptly add silicofluoric acid after, at 50～120 ℃, preferably kept 0.1～24 hour under 70～100 ℃ of stirrings, preferably kept 0.5～5 hour;
6. adding an ammonium nitrate generally is added to few 5g, preferably 10～50g by every 100gY type molecular sieve raw material; Keep the suitable reaction times, promptly add an ammonium nitrate after, keep certain temperature, generally, kept 0.1～24 hour under stirring at 50～120 ℃, preferably kept 0.5～5 hour;
7. separate after an ammonium nitrate is handled, washing, filtration, drying and other steps obtain final modified Y molecular sieve.
Adopt method of the present invention that Y zeolite is handled, can make the Na of Y zeolite 2O content is reduced to below 0.2% (weight), and correspondingly improves SiO 2/ Al 2O 3Ratio, its percent crystallinity can keep 60% at least, generally can keep more than 80% even 90%.In addition, those skilled in the art can wait the Na that regulates the product Y zeolite through ratio and the treatment condition of adjusting raw material an ammonium nitrate and silicofluoric acid according to the inventive method 2O content and SiO 2/ Al 2O 3Character such as molecular ratio, thus obtain meeting the product of different needs.For example, the product that sodium content is low if desired, silica alumina ratio is high then can suitably improve an ammonium nitrate and silicofluoric acid consumption and the suitable severity that improves treatment condition; Sodium content, the relative high product of silica alumina ratio if desired, otherwise then.
Further specify the inventive method and effect below by instance.
Instance 1
Take by weighing raw material NaY-1 molecular sieve (Na 2O content 9.67wt%, silica alumina ratio 5.33, lattice constant ) 2060.6g, put into anticorrosion white steel drum.With 10L zero(ppm) water making beating, and under agitation condition heat temperature raising to 95 ℃, drip 1mol/L fluorine silicic acid aqueous solution 3.5L with even velocity; Dropwised with 2 hour time, this rear slurry was kept 2 hours under 95 ℃ of agitation conditions, added an ammonium nitrate 80g; Stir half a hour; Stop then stirring leave standstill about 10 minutes after, isolate fluorine (silicon) the ammonium aluminate sodium crystal that is deposited in self-control steel drum bottom with decantation, and through washing, dry after recovery.The NaY-1 molecular sieve after the modification and the main physico-chemical property of low-Na and high-Si Y-type molecular sieve see Table 1.Can find out that from table 1 low-Na and high-Si Y-type molecular sieve for preparing with the inventive method has characteristics such as low sodium, high silicon, high-crystallinity and high thermal stability.
Instance 2
Take by weighing raw material NaY-2 molecular sieve (Na 2O content 10.60wt%, silica alumina ratio 3.60, lattice constant
Figure BSA00000180972300052
) 2852.2g, put into anticorrosion white steel drum.With 10L zero(ppm) water making beating, and under agitation condition heat temperature raising to 85 ℃, drip by 3.5 liters of 0.5mol/L fluorine silicic acid aqueous solutions with even velocity; Dropwised with 3 hour time, this rear slurry was kept 12 hours under 55 ℃ of agitation conditions, added an ammonium nitrate 100g; Stir half a hour; Stop then stirring leave standstill about 30 minutes after, isolate fluorine (silicon) the ammonium aluminate sodium crystal that is deposited in from the steel drum bottom with decantation, and through washing, dry after recovery.The NaY-2 molecular sieve after the modification and the main physico-chemical property of low-Na and high-Si Y-type molecular sieve see Table 1.
Product low-Na and high-Si Y-type molecular sieve analytical results shows, its Na 2O content is less than 0.1wt%, SiO 2/ Al 2O 3Molecular ratio 11.85, lattice constant
Figure BSA00000180972300053
Relative crystallinity 108%, 1116 ℃ of DTA structure deteriorate peak temperatures, specific surface area 858m 2/ g, pore volume 0.367mL/g, infrared acidity B acid 1.577mmol/g, L acid 0.084mmol/g, total acid 1.661mmol/g.
Comparative example
Take by weighing 269.8g NH 4NaY molecular sieve raw material (calcination loss of weight 26%, Na 2O content 4.7wt%, SiO 2/ Al 2O 3Molecular ratio 5.07) puts into 2000mL there-necked flask-pull an oar with 1200mL zero(ppm) water; And under the refluxing and stirring condition heat temperature raising to 95 ℃, then under 95 ℃ of constant temperature refluxing and stirring conditions, added once with per 5 minutes, the speed of each 2.5g is added to 90.0g ammonium hexafluorosilicate crystal in the above-mentioned slurries; And rear slurry continues to stir 2 hours under 95 ℃ of constant temperature reflux conditionss; Left standstill about 10 minutes after stopping to stir, the molecular sieve pulp of pouring out the upper strata with decantation carries out hot suction filtration, and with 6 liters of hot distilled water flushings; Take out filter cake then, through dry that products molecule sieves.The product low-Na and high-Si Y-type molecular sieve that makes is through analysis revealed, its Na 2O content 0.16wt%, SiO 2/ Al 2O 3Molecular ratio 11.75, lattice constant does
Figure BSA00000180972300061
Relative crystallinity is 90%, and DTA structure deteriorate peak temperature is 1095 ℃.
Figure BSA00000180972300062
Can find out that from table 1 present method can significantly reduce the Na content of molecular sieve, and improve silica alumina ratio, lattice constant reduces, and the structure deteriorate temperature is not less than 1000 ℃.

Claims (10)

1. high-Si Y-type molecular sieve preparation method, comprise following content: with NaY type molecular sieve is raw material, and NaY type molecular sieve is processed slurries, at first carries out silicofluoric acid and handles, the silicofluoric acid consumption is that every 100g NaY type molecular sieve raw material is more than 0.05 mole; Silicofluoric acid is handled the back and is directly added ammonium salt, and the ammonium salt consumption is added to by every 100gY type molecular sieve raw material and is 5g less; Ammonium salt separates after handling, and obtains the modification high-Si Y-type molecular sieve.
2. according to the described method of claim 1, it is characterized in that described silicofluoric acid consumption is 0.05～0.5 mole of every 100gNaY type molecular sieve raw material, the ammonium salt consumption is counted 10～50g by every 100gY type molecular sieve raw material.
3. according to the described method of claim 1, it is characterized in that NaY type molecular sieve raw slurry concentration is that every 100mL slurries contain 5～30g raw material Y zeolite.
4. according to the described method of claim 1, the temperature that it is characterized in that molecular sieve modified treating processes is 50～120 ℃.
5. according to the described method of claim 1, the temperature that it is characterized in that molecular sieve modified treating processes is 70～100 ℃.
6. according to the described method of claim 1, it is characterized in that silicofluoric acid adds with the solution form, strength of solution is 0.01～5mol/L.
7. according to claim 1 or 6 described methods, it is characterized in that silicofluoric acid adds speed and per hour adds 0.02～0.1 mole of silicofluoric acid by every 100gY type molecular sieve, under agitation kept 0.1～24 hour after adding silicofluoric acid.
8. according to the described method of claim 7, it is characterized in that silicate fluoride solution is 0.1～2mol/L, under agitation kept 0.5～5 hour after adding silicofluoric acid.
9. according to the described method of claim 1; It is characterized in that silicofluoric acid processing back material need not separate; Directly add ammonium salt; Ammonium salt adopts solution or solid form to add, and ammonium salt is an ammonium nitrate, ammonium acetate, volatile salt, bicarbonate of ammonia, ammonium sulfate or ammonium chloride, under agitation keeps 0.1～24 hour behind the adding ammonium salt.
10. according to the described method of claim 1, under agitation to keep 0.5～5 hour after it is characterized in that adding ammonium salt, ammonium salt is an an ammonium nitrate.
CN 201010222388 2010-07-07 2010-07-07 Method for preparing high-silicon Y-type molecular sieves Active CN102311129B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN 201010222388 CN102311129B (en) 2010-07-07 2010-07-07 Method for preparing high-silicon Y-type molecular sieves

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN 201010222388 CN102311129B (en) 2010-07-07 2010-07-07 Method for preparing high-silicon Y-type molecular sieves

Publications (2)

Publication Number Publication Date
CN102311129A true CN102311129A (en) 2012-01-11
CN102311129B CN102311129B (en) 2013-06-19

Family

ID=45424742

Family Applications (1)

Application Number Title Priority Date Filing Date
CN 201010222388 Active CN102311129B (en) 2010-07-07 2010-07-07 Method for preparing high-silicon Y-type molecular sieves

Country Status (1)

Country Link
CN (1) CN102311129B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103773467A (en) * 2012-10-24 2014-05-07 中国石油化工股份有限公司 Method for producing lubricant base oil by hydrogenation isomerization dewaxing

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1056473A (en) * 1990-05-16 1991-11-27 中国石油化工总公司抚顺石油化工研究院 A kind of preparation method of low-Na and high-Si Y-type molecular sieve
CN1323769A (en) * 2000-05-12 2001-11-28 中国石油化工集团公司 Transalkylation catalyst and its prepn.
CN101723400A (en) * 2008-10-29 2010-06-09 中国石油化工股份有限公司 Small crystal grain Y-shaped molecular sieve and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1056473A (en) * 1990-05-16 1991-11-27 中国石油化工总公司抚顺石油化工研究院 A kind of preparation method of low-Na and high-Si Y-type molecular sieve
CN1323769A (en) * 2000-05-12 2001-11-28 中国石油化工集团公司 Transalkylation catalyst and its prepn.
CN101723400A (en) * 2008-10-29 2010-06-09 中国石油化工股份有限公司 Small crystal grain Y-shaped molecular sieve and preparation method thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103773467A (en) * 2012-10-24 2014-05-07 中国石油化工股份有限公司 Method for producing lubricant base oil by hydrogenation isomerization dewaxing
CN103773467B (en) * 2012-10-24 2015-12-02 中国石油化工股份有限公司 A kind of hydroisomerization dewax produces the method for lubricant base

Also Published As

Publication number Publication date
CN102311129B (en) 2013-06-19

Similar Documents

Publication Publication Date Title
CN102745708B (en) Synthetic method of mesoporous-microporous molecular sieve by raising hydrothermal stability
CN107001056B (en) Mesoporous zeolite is prepared with the processing of reduction
CN107555446B (en) Preparation method of hierarchical pore Y-type molecular sieve
CN101723400B (en) Small crystal grain Y-shaped molecular sieve and preparation method thereof
CN102627287B (en) Method for synthesizing molecular sieve under solvent-free condition through grinding solid phase raw materials
CN100572275C (en) A kind of method of modifying of Y molecular sieve
CN101172259B (en) Method for preparing carrier material
CN105056928B (en) A kind of preparation method of controllable hole structure sial composite oxides
CN101898144A (en) Catalytic cracking catalyst of Y-type molecular sieve containing skeleton heteroatom and preparation method thereof
CN103073024A (en) Modified Y-type molecular sieve and preparation method thereof
CN102502687A (en) Method for greenly synthesizing Ti-Si molecular sieve
CN1026313C (en) Process for preparing low-Na and high-Si Y-type molecular sieve
CN103394368A (en) Light oil type hydrocracking catalyst with composite molecular sieve as well as preparation method and application thereof
KR20150031228A (en) Aluminum silicate and method for producing same
CN105271299B (en) A kind of preparation method of the zeolites of mesoporous ZSM 5
CN104591214A (en) Small grain Y type molecular sieve and its preparation method
CN102773117A (en) Medium-oil-type hydrocracking catalyst and preparation method thereof
CN110342535A (en) A kind of preparation method for the porous HZSM-5 zeolite molecular sieve that soda acid is modified
CN106395848A (en) Method for synthesizing molecular sieve with MWW structure from fluosilicic acid and application of molecular sieve
CN104386707A (en) Synthesis method of ultralow-sodium high-silicon nano ZSM-5 molecular sieve
CN102311129B (en) Method for preparing high-silicon Y-type molecular sieves
CN101239325B (en) Montmorillonite/ZSM-5 molecular sieve composite material and preparation thereof
CN107089668A (en) A kind of preparation method of Y-shaped molecular sieve containing rare earth
CN103449465B (en) Beta zeolite prepared through in-situ crystallization of kaolin microspheres, and preparation method thereof
CN105195217B (en) A kind of catalytic cracking catalyst and its preparation method and application

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant