CN105478160B - A kind of method of modifying of ferrierite and a kind of ferrierite and its application - Google Patents
A kind of method of modifying of ferrierite and a kind of ferrierite and its application Download PDFInfo
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- CN105478160B CN105478160B CN201410483078.3A CN201410483078A CN105478160B CN 105478160 B CN105478160 B CN 105478160B CN 201410483078 A CN201410483078 A CN 201410483078A CN 105478160 B CN105478160 B CN 105478160B
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- 229910001657 ferrierite group Inorganic materials 0.000 title claims abstract description 156
- 238000000034 method Methods 0.000 title claims abstract description 115
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 61
- 238000012986 modification Methods 0.000 claims abstract description 43
- 230000004048 modification Effects 0.000 claims abstract description 43
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000006317 isomerization reaction Methods 0.000 claims abstract description 27
- 150000001875 compounds Chemical class 0.000 claims abstract description 17
- 150000001336 alkenes Chemical class 0.000 claims abstract description 6
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 239000002253 acid Substances 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 7
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 7
- 229910052731 fluorine Inorganic materials 0.000 claims description 7
- 239000011737 fluorine Substances 0.000 claims description 7
- 239000011777 magnesium Substances 0.000 claims description 7
- 229910052749 magnesium Inorganic materials 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- 229910021536 Zeolite Inorganic materials 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 6
- 239000010457 zeolite Substances 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 2
- 239000001630 malic acid Substances 0.000 claims description 2
- 235000011090 malic acid Nutrition 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 33
- 239000000758 substrate Substances 0.000 abstract description 12
- 230000008901 benefit Effects 0.000 abstract description 7
- 238000009776 industrial production Methods 0.000 abstract description 4
- 238000012545 processing Methods 0.000 description 35
- 239000000243 solution Substances 0.000 description 20
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 18
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 18
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 15
- 239000002808 molecular sieve Substances 0.000 description 14
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 14
- 229910001220 stainless steel Inorganic materials 0.000 description 14
- 239000010935 stainless steel Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 8
- 238000007493 shaping process Methods 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000010306 acid treatment Methods 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000004575 stone Substances 0.000 description 4
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- ZHPNWZCWUUJAJC-UHFFFAOYSA-N fluorosilicon Chemical compound [Si]F ZHPNWZCWUUJAJC-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 241000219782 Sesbania Species 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000005906 dihydroxylation reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- FGHSTPNOXKDLKU-UHFFFAOYSA-N nitric acid;hydrate Chemical compound O.O[N+]([O-])=O FGHSTPNOXKDLKU-UHFFFAOYSA-N 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- -1 alkene Hydrocarbon Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000007233 catalytic pyrolysis Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000009490 roller compaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- NUMQCACRALPSHD-UHFFFAOYSA-N tert-butyl ethyl ether Chemical compound CCOC(C)(C)C NUMQCACRALPSHD-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Landscapes
- Catalysts (AREA)
Abstract
The ferrierite and its application, this method of the modification obtained the invention discloses a kind of method of modifying of ferrierite and by this method include：Under solution condition, ferrierite to be modified is carried out first with ammonium-containing compound and contacted, the ammonium-containing compound includes ammonium nitrate and ammonium fluosilicate.The modified ferrierite obtained by the method for modifying of the present invention is used for isomerization reaction, particularly it is used to that the conversion ratio of reaction substrate and the selectivity of product can be significantly improved during olefin isomerization, and the method for modifying of the present invention has the advantages of method is simple, cost is relatively low and is suitable for industrial production.
Description
Technical field
The present invention relates to a kind of method of modifying of ferrierite and a kind of ferrierite and its application.
Background technology
In recent years, because the appearance of every environmental protection policy, unleaded gas are promoted the use of, the high-octane rating such as MTBE, ETBE
The demand of additive increases rapidly in the whole world, and raw material of the isobutene as production methyl tertiary butyl ether(MTBE), demand also increases severely therewith.
In addition the utilization of isobutene downstream product so that the isobutene of conventional petroleum catalytic pyrolysis production is current far from meeting
Demand, therefore expand the source of isobutene, increase the yield of isobutene, turn into the task of top priority of current oil development of chemical industry.
At present, method such as sulfuric acid extraction, resin evaporation, tert-butyl alcohol dehydration method, the dehydrogenation of isobutane of isobutene are produced
Method etc. is because problem of environmental pollution, equipment corrosion problem, conversion ratio problem etc. without promoting on a large scale.1977,
Snamprogetti companies develop isomerization of butene technique.Nowadays, n-butene skeletal isomerization method is broadly divided into aluminum oxide work
Skill and molecular sieve technique, and zeolite molecular sieve catalyst is because steady with preferable heat endurance, hydro-thermal in Isomerization of butene
Corrosion-free in qualitative, high anti-poisoning capability and course of reaction, three wastes problem, it is easy to operate continuously and welcome extensively.
Therefore developing high performance isomerization of butene molecular sieve catalyst has huge economic interests and social benefit.
Molecular sieve, the hole and duct of arranged regular are included in its crystal structure.Intracrystalline pore footpath is that molecular number magnitude is big
It is small, diameter molecule less than that can only be allowed to enter, can be different by molecular size different even boiling point, polarity and degree of saturation
Molecule separate, that is, play the role of " to sieve " molecule, therefore claim molecular sieve.Can basis source, duct size, skeleton member
Element composition etc. is classified.
In order that must participate in the molecular sieve of specific reaction can reach required reaction result, those skilled in the art are usual
Molecular sieve is modified using steam treatment or acid treatment means.Wherein, steam treatment can make molecular sieve while send out
Raw dealuminzation and dehydroxylation, therefore be the important modification method of zeolite molecular sieve catalyst.But using steam treatment hand
The non-framework aluminum that can usually cause to remove on the skeleton of molecular sieve during section processing molecular sieve blocks duct, so as to influence molecule diffusion
And catalytic performance；And dehydroxylation can then cause the acid amount of molecular sieve and acid strength to reduce.
The means of acid treatment can reduce the content of non-framework aluminum, the degree of opening in duct be improved, after peracid treatment
The acid amount of molecular sieve and acid strength increase, so that the probability increase of effective collision, reaction occur with acid site for reaction substrate
Conversion ratio can correspondingly increased.However, the selectivity of reaction substrate usually reduces with the enhancing of acidic zeolite.
Even and the prior art for the US5523510 for being combined acid treatment and steam treatment can similarly be taken off due to molecular sieve
Aluminium is serious and causes the conversion ratio of reaction and selectivity relatively low.Therefore, at the conventional use of vapor of those skilled in the art
Reason means and/or acid treatment means can not obtain the catalyst with excellent properties desired by researchers.
The content of the invention
It is an object of the invention to provide a kind of method of modifying of ferrierite, by what is obtained by the method for modifying of the present invention
Modified ferrierite is used for isomerization reaction, particularly for olefin isomerization when can significantly improve turning for reaction substrate
The selectivity of rate and product, and the method for modifying of the present invention has that method is simple, cost is relatively low and is suitable for industry
The advantages of production.
To achieve these goals, on the one hand, the present invention provides a kind of method of modifying of ferrierite, and this method includes：
Under solution condition, ferrierite to be modified is carried out first with ammonium-containing compound and contacted, the ammonium-containing compound includes nitre
Sour ammonium and ammonium fluosilicate.
On the other hand, a kind of magnesium alkali for the modification that the present invention also provides above-mentioned method of modifying by the present invention to obtain boils
Stone.
The third aspect, a kind of magnesium alkali for the modification that the present invention also provides above-mentioned method of modifying by the present invention to obtain boil
Application of the stone in isomerisation of olefin.
By the way that the ferrierite of the modification obtained using the above-mentioned method of modifying of the present invention is used for into isomerization reaction, especially
The conversion ratio of reaction substrate and the selectivity of product can be significantly improved when being for olefin isomerization, for example, from originally
The result of the embodiment of invention can be seen that when the ferrierite of modification of the present invention is used for into n-butene isomerization reaction, energy
Enough so that the conversion ratio of n-butene reaches more than 35%, and the selectivity of isobutene reaches more than 92%.Moreover, the present invention's changes
Property method also there is the advantages of method is simple, cost is relatively low and is suitable for industrial production.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
In the present invention, described " first ", " second ", " the 3rd ", " the 4th ", " the 5th " and " 6th " is without successively suitable
Sequence, the present invention merely to distinguish and it is so named, it is limitation of the present invention that those skilled in the art, which should not be construed as this,.
On the one hand, the invention provides a kind of method of modifying of ferrierite, this method to include：, will under solution condition
Ferrierite to be modified carries out first with ammonium-containing compound and contacted, and the ammonium-containing compound includes ammonium nitrate and ammonium fluosilicate.
In the present invention, the solution condition is known to those skilled in the art, and the present invention will not be repeated here, this hair
Exemplarily used in bright embodiment and above-mentioned modification is carried out under aqueous conditions.
In method of the present invention, the weight ratio of the ferrierite to be modified and ammonium-containing compound can be 1：
0.1-15；Preferably 1：0.8-8.In the present invention, the weight of the ammonium-containing compound is the weight of ammonium nitrate and ammonium fluosilicate
Sum.
In method of the present invention, the dosage of the ammonium-containing compound allows the ammonium concentration in the solution to be
0.01-2mol/L；Preferably 0.1-1.5mol/L.In the present invention, the ammonium concentration in the solution refers to, when in solution condition
Under, after the ammonium-containing compound is added into system, the concentration of the ammonium ion in solution.
Under preferable case, in method of the present invention, the weight ratio of the ammonium nitrate and ammonium fluosilicate can be 1：
0.5-1.6；More preferably can be 1：0.8-1.4.It was found by the inventors of the present invention that under the same conditions, when ammonium nitrate and fluorine silicon
The weight ratio of sour ammonium is 1：When in the range of 0.5-1.6, the ferrierite for the modification that can to obtain is for isomerization reaction
The substrate conversion efficiency and selectivity of product of optimization are obtained when middle, and when both weight ratios are 1：, can when in the range of 0.8-1.4
To cause the effect above to be optimal.And when the weight ratio of ammonium nitrate and ammonium fluosilicate is less than 1：When 1.6, the conversion ratio of substrate compared with
It is high and the selectivity of product can decline；When the weight of ammonium nitrate and ammonium fluosilicate ratio is more than 1：When 0.5, the conversion ratio of substrate
Relatively low and product selectivity is higher.
Under preferable case, in method of the present invention, the condition of first contact includes：The temperature of contact is
60-120℃；Preferably 70-100 DEG C.
Under preferable case, in method of the present invention, the condition of first contact includes：The time of contact is 6-
12h；Preferably 6-10h.
, can be with after the ferrierite and ammonium-containing compound, which carry out first, to be contacted in method of the present invention
The step of including resulting ferrierite to be dried and be calcined successively.In method of the present invention, it will preferably enter
The ferrierite that row first obtains after contacting carries out subsequent step again after being dried and be calcined successively.
In method of the present invention, the temperature of preferably described drying is 80-150 DEG C, and the time of the drying is 6-
12h。
In method of the present invention, the temperature of preferably described roasting is 400-600 DEG C, and the time of the roasting is 2-
8h。
Under preferable case, in method of the present invention, this method can include：In ferrierite and nitre to be modified
Before the sour contact of ammonium and ammonium fluosilicate progress first and/or after the first contact, ferrierite and vapor and air are carried out
Second contact.
That is, in method of the present invention, this method can include：
The first preferred embodiment：The ferrierite first is carried out into second with vapor and air to contact, then
The ferrierite to be modified obtain after the second contact is carried out into first with ammonium nitrate and ammonium fluosilicate again to contact；Or
Second of preferred embodiment：Ferrierite to be modified first is carried out into first with ammonium nitrate and ammonium fluosilicate to connect
Touch, resulting ferrierite then is carried out into second with vapor and air again contacts；Or
The third preferred embodiment：The ferrierite first is carried out into second with vapor and air to contact, then
The ferrierite to be modified obtain after the second contact is carried out into first with ammonium nitrate and ammonium fluosilicate to contact, again finally
Resulting ferrierite is carried out into second with vapor and air to contact.
Under preferable case, in method of the present invention, the ferrierite carries out second with vapor and air and connect
Tactile condition can include：Relative to every 100g ferrierite, flow rates 0.027-0.2mol/min, it is more preferably
0.055-0.14mol/min。
Under preferable case, in method of the present invention, the ferrierite carries out second with vapor and air and connect
Tactile condition can include：The time of contact is 1-8h, more preferably 1.5-6h.
Under preferable case, in method of the present invention, the ferrierite carries out second with vapor and air and connect
Tactile condition can include：The temperature of contact is 450-650 DEG C, 500-620 DEG C.
Under preferable case, in method of the present invention, the ferrierite carries out second with vapor and air and connect
Tactile condition can include：The mol ratio of vapor and air is 1：1-3, in the present invention, the vapor and air rub
You are than the mol ratio for the water and air under normal temperature (25 DEG C), that is, in the present invention, the vapor is by the way that water is added
Heat and obtain, above-mentioned mol ratio is the mol ratio of the dosage of water and the dosage of air under normal temperature.
In method of the present invention, it can include material resulting after the contact of progress second in dry conditions
Cooled down, subsequent step is carried out again after material cooling.
In method of the present invention, second contact can be carried out several times.That is, can be first by described in
Ferrierite carries out second with vapor and air and contacts the suitable time, then enters resulting material in dry conditions
Row cooling；It is carried out second with vapor and air again after material cooling and contacts the suitable time, and in dry conditions
Cooled down, it is so repeated multiple times.In method of the present invention, it can preferably carry out 1-5 times.If second is carried out several times
Contact, then the time of above-mentioned contact is the summation of the time of each second contact.
In method of the present invention, this method can include：In ferrierite to be modified and ammonium nitrate and fluorine silicon
Before the sour contact of ammonium progress first or after the first contact, ferrierite is carried out the 3rd with acid and contacted.
That is, in method of the present invention, this method can include：
4th kind of preferred embodiment：Ferrierite first is carried out into the 3rd with acid to contact, then will carry out the 3rd contact
The ferrierite to be modified obtained afterwards carries out first with ammonium nitrate and ammonium fluosilicate and contacted；Or
5th kind of preferred embodiment：Ferrierite to be modified first is carried out into first with ammonium nitrate and ammonium fluosilicate to connect
Touch, resulting ferrierite then is carried out into the 3rd with acid again contacts.
Under preferable case, in method of the present invention, the condition of the 3rd contact includes：The temperature of contact is
20-100℃；More preferably 20-80 DEG C.
Under preferable case, in method of the present invention, the condition of the 3rd contact includes：The time of contact is 1-
6h；More preferably 2-5h.
In method of the present invention, the sour concentration can be 1-10 weight %, preferably 3-7 weight %.
In method of the present invention, the acid can be organic acid or inorganic acid, and the present invention preferably acid can
Think at least one of nitric acid, hydrochloric acid, acetic acid, citric acid and malic acid.
In method of the present invention, will preferably carry out obtained material after the 3rd contact be washed with water at least twice after
Processing is dried, the ferrierite obtained after drying process is used for subsequent step.The present invention does not have to the temperature of the drying
There is special restriction, exemplarily used in embodiment of the invention and processing is dried at 120 DEG C.
In method of the present invention, preferably described ferrierite to be modified can be ZSM-23, ZSM-35 and
At least one of ZSM-38.
According to the 6th kind of preferred embodiment, method of the invention can also include：
First the ferrierite to be modified with acid the 3rd contact, after the completion of the 3rd contact, the thing that will obtain
Material is washed with water at least twice, and processing is dried at 120 DEG C；Then the ferrierite and nitric acid to be modified that will be obtained
Ammonium and ammonium fluosilicate carry out the first contact, and are dried and are calcined successively；Finally resulting ferrierite and water are steamed again
Gas and air carry out the second contact, and are cooled down in dry conditions.In the preferred embodiment, described first connects
The condition of tactile, the second contact and the 3rd contact is as it was previously stated, the present invention will not be repeated here.
In method of the present invention, the magnesium alkali for the modification that can also include obtaining after above-mentioned modification boils
The step of stone is molded, the present invention to the shaping the step of there is no particular limitation, those skilled in the art can use
Various methods commonly used in the art are molded, and are exemplarily listed using such as lower section in embodiment of the invention
The ferrierite of modification of the method to being obtained is molded：
By the ferrierite of appropriate modification, binding agent such as alumina powder, extrusion aid and expanding agent such as sesbania powder
Be added to methylcellulose in kneading machine, after stirring add nitric acid the aqueous solution, continue stirring it is uniform to material, then will obtain
The material obtained is placed in roller-compaction in banded extruder, is then placed in the material obtained after shaping and conserves such as 6h at room temperature, then
It is dried overnight at such as 120 DEG C, and such as 5h is calcined at such as 500 DEG C.Herein it should be strongly noted that the present invention only
It is the method for exemplarily listing above-mentioned shaping, this should not be interpreted as to technical scheme by those skilled in the art
Limitation.
On the other hand, present invention also offers a kind of above-mentioned method of modifying by the present invention and the magnesium alkali of modification that obtains
Zeolite.
The ferrierite of the modification obtained using the above method of the present invention is used for isomerization reaction, particularly for alkene
Hydrocarbon isomerization can significantly improve the conversion ratio of reaction substrate and the selectivity of product, and the modification side of the present invention when reacting
Method has the advantages of method is simple, cost is relatively low and is suitable for industrial production.
The third aspect, present invention also offers a kind of above-mentioned method of modifying by the present invention and the magnesium alkali of modification that obtains
Application of the zeolite in isomerisation of olefin.
There is no particular limitation for condition of the present invention to the isomerization reaction, and those skilled in the art can will pass through this
The ferrierite that the above method of invention obtains is used in various isomerization reactions, in especially preferred cases, will can lead to
The ferrierite for crossing the above method acquisition of the present invention is used in the reaction of n-butene isomerization.The magnesium alkali boiling of the modification of the present invention
There is no particular limitation to reaction condition of the n-butene isomerization etc. for stone, and those skilled in the art can be according to conventional progress
The condition of the reaction of n-butene isomerization is selected.Such as in an embodiment of the present invention, exemplarily with the following method
Carry out n-butene isomerization reaction：
Under 400 DEG C and normal pressure so that reaction substrate passes through the ferrierite containing modification of the present invention
10mL fixed bed reactors, and mass space velocity (WHSV) is 4h-1, the volume ratio of nitrogen and n-butene is 1.The present invention is to being made
There is no particular limitation for the ferrierite of modification and the amount ratio of reaction substrate, and those skilled in the art can be according to reality
Need to be selected.Herein it should be strongly noted that the present invention is only exemplarily to list the modification using the present invention
This should not be interpreted as to technical scheme by the method that ferrierite carries out n-butene isomerization, those skilled in the art
Limitation.
The present invention will be described in detail by way of examples below.In following examples, in the feelings being not particularly illustrated
Under condition, used various reagents are all from commercially available.In the examples below, used water is deionized water.
Embodiment 1
The present embodiment is using method of modifying provided by the invention processing ferrierite, to obtain modified ferrierite.
Modification：Take 90g sodium form ferrierites ZSM-23 (be purchased from Shanghai Shen Tan environmental friendly materials Co., Ltd, under
Together), it is added in the solution of 1000mL ammonium nitrate containing 32g and 35.4g ammonium fluosilicates, the contact processing 8h, Zhi Houleng at 85 DEG C
But, filter, 100 DEG C of dry 10h, 500 DEG C of roasting 4h, obtain modified ferrierite 1-A.
Embodiment 2
The present embodiment is using method of modifying provided by the invention processing ferrierite, to obtain modified ferrierite.
Modification：90g sodium form ferrierites ZSM-35 (being purchased from Dalian Ke Teli Chemical Co., Ltd.s, similarly hereinafter) is taken, is added
Enter into the solution of 1000mL ammonium nitrate containing 55.4g and 72g ammonium fluosilicates, the contact processing 7h at 95 DEG C, afterwards cooling, mistake
Filter, 120 DEG C of dry 8h, 400 DEG C of roasting 6h, obtain modified ferrierite 2-A.
Embodiment 3
The present embodiment is using method of modifying provided by the invention processing ferrierite, to obtain modified ferrierite.
Modification：Take 90g sodium form ferrierites ZSM-38 (be purchased from Shanghai Shen Tan environmental friendly materials Co., Ltd, under
Together), it is added in the solution of 1000mL ammonium nitrate containing 9.4g and 7.6g ammonium fluosilicates, the contact processing 10h, Zhi Houleng at 75 DEG C
But, filter, 90 DEG C of dry 12h, 600 DEG C of roasting 3h, obtain modified ferrierite 3-A.
Embodiment 4
The present embodiment is using method of modifying provided by the invention processing ferrierite, to obtain modified ferrierite.
Modification：
(1) 90g sodium form ferrierite ZSM-23 are taken, is placed in vertical stainless steel tube, is heated to 600 in air atmosphere
DEG C, adjust the intake of air, by water (0.056mol/min) as water vapor with air (0.056mol/min) together
By the ferrierite 2h in stainless steel tube, then cool down in dry air, be so repeated 3 times.
(2) ferrierite that above-mentioned steps of learning from else's experience (1) obtain afterwards, 1000mL ammonium nitrate containing 32g and 35.4g fluorine are added to
In the solution of ammonium silicate, the contact processing 8h at 85 DEG C, cool down, filter, 100 DEG C of dry 10h afterwards, 500 DEG C of roasting 4h, obtain
Modified ferrierite 4-A.
Embodiment 5
The present embodiment is using method of modifying provided by the invention processing ferrierite, to obtain modified ferrierite.
Modification：
(1) 90g sodium form ferrierite ZSM-35 are taken, are added to the molten of 1000mL ammonium nitrate containing 55.4g and 72g ammonium fluosilicates
In liquid, the contact processing 7h at 95 DEG C, cool down, filter, 120 DEG C of dry 8h afterwards, 400 DEG C of roasting 6h.
(2) ferrierite that above-mentioned steps of learning from else's experience (1) obtain afterwards, is placed in vertical stainless steel tube, in air atmosphere
Be heated to 550 DEG C, adjust the intake of air, by water (0.067mol/min) as water vapor with air (0.134mol/
Min) then cool down in dry air, be so repeated 4 times by the ferrierite 1.5h in stainless steel tube together.Obtain
Modified ferrierite 5-A.
Embodiment 6
The present embodiment is using method of modifying provided by the invention processing ferrierite, to obtain modified ferrierite.
Modification：
(1) 90g sodium form ferrierite ZSM-38 are taken, is placed in vertical stainless steel tube, is heated to 520 in air atmosphere
DEG C, adjust the intake of air, by water (0.044mol/min) as water vapor with air (0.132mol/min) together
By the ferrierite 2h in stainless steel tube, then cool down in dry air, be so repeated 2 times.
(2) ferrierite that above-mentioned steps of learning from else's experience (1) obtain afterwards, 1000mL ammonium nitrate containing 9.4g and 7.6g fluorine are added to
In the solution of ammonium silicate, the contact processing 10h at 75 DEG C, cool down, filter, 90 DEG C of dry 12h afterwards, 600 DEG C of roasting 3h.
(3) ferrierite that above-mentioned steps of learning from else's experience (2) obtain afterwards, is placed in vertical stainless steel tube, in air atmosphere
Be heated to 530 DEG C, adjust the intake of air, by water (0.072mol/min) as water vapor with air (0.18mol/
Min) then cooled down together by the ferrierite 5h in stainless steel tube in dry air.Obtain modified ferrierite
6-A。
Embodiment 7
The present embodiment is using method of modifying provided by the invention processing ferrierite, to obtain modified ferrierite.
Modification：
(1) take 90g sodium form ferrierites ZSM-23, at 40 DEG C, 3h, Ran Houyong are handled with 6 weight % aqueous solution of nitric acid
Water washing 2 times.
(2) ferrierite that above-mentioned steps of learning from else's experience (1) obtain afterwards, 1000mL ammonium nitrate containing 32g and 35.4g fluorine are added to
In the solution of ammonium silicate, the contact processing 8h at 85 DEG C, cool down, filter, 100 DEG C of dry 10h afterwards, 500 DEG C of roasting 4h, obtain
Modified ferrierite 7-A.
Embodiment 8
The present embodiment is using method of modifying provided by the invention processing ferrierite, to obtain modified ferrierite.
Modification：
(1) 90g sodium form ferrierite ZSM-35 are taken, are added to the molten of 1000mL ammonium nitrate containing 55.4g and 72g ammonium fluosilicates
In liquid, the contact processing 7h at 95 DEG C, cool down, filter, 120 DEG C of dry 8h afterwards, 400 DEG C of roasting 6h.
(2) ferrierite that above-mentioned steps of learning from else's experience (1) obtain afterwards, at 50 DEG C, handled with 7 weight % aqueous solution of nitric acid
2h, then it is washed with water 2 times.Obtain modified ferrierite 8-A.
Embodiment 9
The present embodiment is using method of modifying provided by the invention processing ferrierite, to obtain modified ferrierite.
Modification：
(1) take 90g sodium form ferrierites ZSM-23, at 50 DEG C, 2h, Ran Houyong are handled with 3 weight % aqueous solution of nitric acid
Water washing 2 times.
(2) ferrierite that above-mentioned steps of learning from else's experience (1) obtain afterwards, 1000mL ammonium nitrate containing 32g and 35.4g fluorine are added to
In the solution of ammonium silicate, the contact processing 8h at 85 DEG C, cool down, filter, 100 DEG C of dry 10h afterwards, 500 DEG C of roasting 4h.
(3) ferrierite that above-mentioned steps of learning from else's experience (2) obtain afterwards, is placed in vertical stainless steel tube, in air atmosphere
Be heated to 550 DEG C, adjust the intake of air, by water (0.061mol/min) as water vapor with air (0.122mol/
Min) then cooled down together by the ferrierite 6h in stainless steel tube in dry air.Obtain modified ferrierite
9-A。
Embodiment 10
The present embodiment is using method of modifying provided by the invention processing ferrierite, to obtain modified ferrierite.
Modification：90g sodium form ferrierite ZSM-23 are taken, are added to 1000mL ammonium nitrate containing 26.2g and 42g fluosilicic acid
In the solution of ammonium, the contact processing 8h at 85 DEG C, cool down, filter, 100 DEG C of dry 10h afterwards, 500 DEG C of roasting 4h, be modified
Ferrierite 10-A.
Embodiment 11
The present embodiment is using method of modifying provided by the invention processing ferrierite, to obtain modified ferrierite.
Modification：90g sodium form ferrierite ZSM-23 are taken, are added to 1000mL ammonium nitrate containing 24.4g and 44g fluosilicic acid
In the solution of ammonium, the contact processing 8h at 85 DEG C, cool down, filter, 100 DEG C of dry 10h afterwards, 500 DEG C of roasting 4h, be modified
Ferrierite 11-A.
Embodiment 12
The present embodiment is using method of modifying provided by the invention processing ferrierite, to obtain modified ferrierite.
Modification：90g sodium form ferrierite ZSM-23 are taken, are added to 1000mL ammonium nitrate containing 50.4g and 15.2g fluorine silicon
In the solution of sour ammonium, the contact processing 8h at 85 DEG C, cool down, filter, 100 DEG C of dry 10h afterwards, 500 DEG C of roasting 4h, changed
The ferrierite 12-A of property.
Embodiment 13
The present embodiment is using method of modifying provided by the invention processing ferrierite, to obtain modified ferrierite.
Modification：
(1) ferrierite ZSM-23 to be modified is taken, is placed in vertical stainless steel tube, is heated to 550 in air atmosphere
DEG C, adjust the intake of air, by water (0.061mol/min) as water vapor with air (0.122mol/min) together
By the ferrierite 6h in stainless steel tube, then cooled down in dry air.
(2) ferrierite that above-mentioned steps of learning from else's experience (1) obtain afterwards, 1000mL ammonium nitrate containing 32g and 35.4g fluorine are added to
In the solution of ammonium silicate, the contact processing 8h at 85 DEG C, cool down, filter, 100 DEG C of dry 10h afterwards, 500 DEG C of roasting 4h.
(3) ferrierite that above-mentioned steps of learning from else's experience (2) obtain afterwards, at 50 DEG C, handled with 3 weight % aqueous solution of nitric acid
2h, then it is washed with water 2 times.Obtain modified ferrierite 13-A.
Comparative example 1
The method of modifying processing ferrierite that this comparative example is provided using prior art, to obtain modified ferrierite.
Modification：
(1) 90g sodium form ferrierite ZSM-23 are taken, is placed in vertical stainless steel tube, is heated to 600 in air atmosphere
DEG C, stopping is passed through air, and water is passed through into the ferrierite in stainless steel tube as water vapor with 0.14mol/min speed
2h, then cooled down in dry air.
(2) ferrierite that above-mentioned steps of learning from else's experience (1) obtain afterwards, at 50 DEG C, handled with 3 weight % aqueous solution of nitric acid
2h, then it is washed with water 2 times.Obtain modified ferrierite D-1-A.
Comparative example 2
The method of modifying processing ferrierite that this comparative example is provided using prior art, to obtain modified ferrierite.
Modification：90g sodium form ferrierite ZSM-23 are taken, are added in the solution of 1000mL ammonium nitrate containing 64g, 85
Contact processing 8h at DEG C, cools down, filters, 100 DEG C of dry 10h afterwards, 500 DEG C of roasting 4h, obtains modified ferrierite D-2-
A。
Comparative example 3
The method of modifying processing ferrierite that this comparative example is provided using prior art, to obtain modified ferrierite.
Modification：90g sodium form ferrierite ZSM-23 are taken, are added in the solution of 1000mL ammonium fluosilicates containing 71.2g,
The contact processing 8h at 85 DEG C, cools down, filters, 100 DEG C of dry 10h afterwards, 500 DEG C of roasting 4h, obtains modified ferrierite
D-3-A。
Preparation example 1
The ferrierite of modification that this preparation example is used to obtain in above-described embodiment 1-13 and comparative example 1-3 carry out into
Type, the method for the shaping are as follows：
Take the ferrierite, 20g alumina powders, 4g sesbania powders of 80g modifications to be sequentially added into kneading machine, stir 20min
The mixed solution of 8g nitric acid and 80g water is added afterwards, is continued stirring to material and is well mixed.Be placed in banded extruder rolled, into
Type.Material after shaping is placed in and conserved 6 hours at room temperature, is then dried overnight at 120 DEG C, 500 DEG C are calcined 5 hours.
Test case 1-16
The ferrierite of the modification of the shaping obtained by above-mentioned preparation example 1 is used for n-butene isomerization reaction.Positive fourth
The unstripped gas of isomerizalion reaction evaluating obtains n-butene from Scott special product coal gas, and its content is more than 99.2% (weight), adopts
It is 10mL fixed bed reactors, appreciation condition and evaluation result are shown in Tables 1 and 2 respectively.Wherein, SBET(m2/ g) represent
Specific surface area for the ferrierite of the modification of the shaping of reaction.
Table 1
| Mass space velocity | Reaction pressure | Reaction temperature | N2/ n-butene (volume ratio) |
| 4h-1 | Normal pressure | 400℃ | 1：1 |
It can be seen from the results in table 2 the ferrierite for the modification that the method using the present invention is prepared is used for
During n-butene isomerization reaction, the conversion ratio of n-butene is enabled to even up to reach generally more than more than 35%
44.5%, and the selectivity of product isobutene, more than 92%, highest can reach 97.4%.And from the result of above-mentioned comparative example
As can be seen that under similar conditions, the catalytic activity performance of the ferrierite of the modification obtained using the method for prior art compared with
Difference：The conversion ratio of n-butene is up to 28.1%, and the selectivity of isobutene is up to 78.3%.The above results show, using this
The ferrierite that the above-mentioned method of modifying of invention obtains is used for conversion ratio and the production that substrate can be significantly improved during isomerization reaction
The selectivity of thing.And the method for the present invention has the advantages of simple, cost is relatively low and is suitable for industrial production.
Table 2
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (17)
1. a kind of method of modifying of ferrierite, it is characterised in that this method includes：Under solution condition, by magnesium to be modified
Alkali zeolite carries out first with ammonium-containing compound and contacted, and the ammonium-containing compound includes ammonium nitrate and ammonium fluosilicate, described to be modified
Ferrierite and ammonium-containing compound weight ratio be 1：0.1-15.
2. according to the method for claim 1, wherein, the weight ratio of the ferrierite to be modified and ammonium-containing compound is
1：0.8-8.
3. according to the method for claim 1, wherein, the dosage of the ammonium-containing compound causes the ammonium concentration in the solution
For 0.01-2mol/L.
4. according to the method for claim 1, wherein, the dosage of the ammonium-containing compound causes the ammonium concentration in the solution
For 0.1-1.5mol/L.
5. according to the method described in any one in claim 1-4, wherein, the weight ratio of the ammonium nitrate and ammonium fluosilicate is
1：0.5-1.6.
6. according to the method for claim 5, wherein, the weight ratio of the ammonium nitrate and ammonium fluosilicate is 1：0.8-1.4.
7. according to the method for claim 1, wherein, the condition of first contact includes：The temperature of contact is 60-120
DEG C, the time of contact is 6-12h.
8. according to the method for claim 1, wherein, this method includes：In ferrierite to be modified and ammonium nitrate and fluorine
Before the contact of ammonium silicate progress first and/or after the first contact, ferrierite is carried out second with vapor and air and contacted.
9. according to the method for claim 8, wherein, the ferrierite carries out the second bar contacted with vapor and air
Part includes：Relative to every 100g ferrierite, flow rates 0.027-0.2mol/min, the time of contact is 1-8h,
The temperature of contact is 450-650 DEG C；The mol ratio of vapor and air is 1：1-3.
10. according to the method for claim 1, wherein, this method includes：In ferrierite to be modified and ammonium nitrate and fluorine
Before the contact of ammonium silicate progress first or after the first contact, ferrierite is carried out the 3rd with acid and contacted.
11. according to the method for claim 10, wherein, the condition of the 3rd contact includes：The temperature of contact is 20-
100 DEG C, the time of contact is 1-6h.
12. according to the method for claim 10, wherein, this method includes：First by the ferrierite to be modified and acid
The 3rd contact is carried out, after the completion of the 3rd contact, obtained material is washed with water at least twice, and is being dried；Then
Obtained ferrierite to be modified is carried out into first with ammonium nitrate and ammonium fluosilicate to contact, and is dried and is calcined successively；
Resulting ferrierite finally is carried out into second with vapor and air again to contact, and cooled down in dry conditions.
13. according to the method described in any one in claim 10-12, wherein, the sour concentration is 1-10 weight %.
14. according to the method for claim 13, wherein, the acid is in nitric acid, hydrochloric acid, acetic acid, citric acid and malic acid
At least one.
15. according to the method for claim 1, wherein, the ferrierite to be modified is ZSM-23, ZSM-35 and ZSM-
At least one of 38.
16. the ferrierite for the modification that the method in claim 1-15 described in any one obtains.
17. application of the ferrierite for the modification that the method described in claim 16 obtains in isomerisation of olefin.
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| DE10133175A1 (en) * | 2001-07-07 | 2003-03-06 | Korea Advanced Inst Sci & Tech | Manufacturing method of metal contained binary catalyst for dewaxing process |
| CN103041848A (en) * | 2011-10-17 | 2013-04-17 | 中国石油化工股份有限公司 | Catalyst used for heterogeneously producing isoalkene by utilizing direct-chain olefin skeleton and preparation method thereof |
| CN103418420A (en) * | 2012-05-17 | 2013-12-04 | 巩雁军 | Preparation method and applications of modified ZSM-5 molecular sieve for high-selective preparation of propylene from methanol and dimethyl ether |
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