CN107159307A - A kind of sial phosphorus molecular sieve of carried metal and application - Google Patents
A kind of sial phosphorus molecular sieve of carried metal and application Download PDFInfo
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- CN107159307A CN107159307A CN201710481331.5A CN201710481331A CN107159307A CN 107159307 A CN107159307 A CN 107159307A CN 201710481331 A CN201710481331 A CN 201710481331A CN 107159307 A CN107159307 A CN 107159307A
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- molecular sieve
- phosphorus molecular
- sial phosphorus
- carried metal
- shaping
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 61
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 56
- 239000002184 metal Substances 0.000 title claims abstract description 55
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 53
- 239000011574 phosphorus Substances 0.000 title claims abstract description 53
- 238000007493 shaping process Methods 0.000 claims abstract description 27
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 239000002002 slurry Substances 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 18
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 13
- 239000010703 silicon Substances 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 230000001172 regenerating effect Effects 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims abstract description 9
- 239000004927 clay Substances 0.000 claims abstract description 8
- 230000018044 dehydration Effects 0.000 claims abstract description 8
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 7
- 239000003595 mist Substances 0.000 claims abstract description 7
- 241000269350 Anura Species 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 230000008929 regeneration Effects 0.000 claims description 8
- 238000011069 regeneration method Methods 0.000 claims description 8
- 238000005516 engineering process Methods 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 6
- 239000002689 soil Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 239000004411 aluminium Substances 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- 239000010427 ball clay Substances 0.000 claims description 2
- 239000000440 bentonite Substances 0.000 claims description 2
- 229910000278 bentonite Inorganic materials 0.000 claims description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 2
- 239000000428 dust Substances 0.000 claims description 2
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 230000001737 promoting effect Effects 0.000 claims description 2
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 claims description 2
- URRHWTYOQNLUKY-UHFFFAOYSA-N [AlH3].[P] Chemical compound [AlH3].[P] URRHWTYOQNLUKY-UHFFFAOYSA-N 0.000 claims 1
- 238000005119 centrifugation Methods 0.000 claims 1
- 239000004575 stone Substances 0.000 claims 1
- 239000007789 gas Substances 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 3
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 description 10
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 9
- 229910002091 carbon monoxide Inorganic materials 0.000 description 8
- -1 polypropylene Polymers 0.000 description 7
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 229910001593 boehmite Inorganic materials 0.000 description 5
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical group O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 5
- 238000004587 chromatography analysis Methods 0.000 description 4
- 229910052622 kaolinite Inorganic materials 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 239000000686 essence Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO compounds]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a kind of sial phosphorus molecular sieve of carried metal and application, by 0.01~0.1 part of 10~24 parts of desalted water, 1 part of SAPO, 2.5~4 parts of clay, 0.4~0.9 part of silicon source, 0.7~1.2 part of silicon source and diluted acid, add in batching kettle, be mixed into slurries；Slurries are delivered in shaping tower through centrifugal pump and carry out mist projection granulating shaping；The communicated band of material after shaping is delivered to fill and is stirred in the exchange kettle for exchanging liquid, obtains being loaded with the material of metal；It is then sent to progress filtering means dehydration operation on vacuum belt filter；Material afterwards is collected in collector, is then placed in industrial furnace and is dried roasting, obtains the sial phosphorus molecular sieve of carried metal.CO gases are converted into CO during the present invention can promote alcohol ether olefine reaction regenerative system2, environmental protection, good energy-conserving effect, automaticity is high, is easy to industrialization promotion.
Description
Technical field
The invention belongs to catalyst preparation and applied technical field, more particularly, to a kind of sial phosphorus molecule of carried metal
Sieve and application.
Background technology
Propylene is the basic chemical industry raw material of current large chemical products most important in the world and the economic development of support China
One of, a variety of basic organics can be prepared.Can for example prepare expoxy propane, methacrylaldehyde, propenyl, isopropanol, carbon tetrachloride,
Butanol etc..In recent years, due to being influenceed by downstream derivative thing (especially polypropylene) demand, the demand of propylene significantly increases
Greatly.Due to the shortage of state's inner propene resource, the demand of domestic market far can not be met, the domestic degree of self-sufficiency decline to a great extent, it is necessary to
A large amount of imports.With the environment of international market keen competition, development propylene and its derivatives must use state-of-the-art in the world
Environmentally friendly technology technology, reaches the large-scale economic scale of low cost production, the exploitation prospect of Chinese propylene is very much wide.
For Chinese propylene development prospect, the catalyst for producing propylene with methanol that China Tianchen Engineering Co., Ltd develops is mainly
A kind of sial phosphorus molecular sieve, this molecular sieve can make methanol conversion reach 100% or close to 100%, ethene and propylene
Selectivity more than 78%, almost without C5More than product, and the hydrothermal stability that protrudes of sial phosphorus molecular sieve and suitable
Suitable pore passage structure makes its performance more superior, will turn into and be used widely in the future.
At present, prepared in fluid bed in olefin hydrocarbon, there is CO and CO when often catalyst regenerates in a regenerator2Two
Gas is planted, wherein CO contents account for total gas content 3-7%, and this part is not converted to CO2CO outside row environment can be caused
Pollution, while the energy not discharged in CO can increase the consumption of the regenerator energy again, this just proposes challenge to technology, such as
Fruit can provide a kind of catalyst for not influenceing sial phosphorus molecular sieve performance in alcohol ether olefine reaction fluid bed and improve CO conversions
For CO2Ability, this will reduce the pollution to environment, and consumption of the reduction regenerator to the energy, and this idea becomes
Current field thing urgently to be resolved hurrily.
The content of the invention
In view of this, the present invention is directed to propose a kind of sial phosphorus molecular sieve of carried metal and application, promote alcohol ether alkene
CO gases are converted into CO during hydrocarbon reaction regenerative system2, environmental protection, good energy-conserving effect, automaticity is high, is easy to industry
Change and promote.
To reach above-mentioned purpose, the technical proposal of the invention is realized in this way：
A kind of sial phosphorus molecular sieve of carried metal, is prepared from by following steps：
The first step：The component of following quality parts ratio is sequentially added in batching kettle：10~24 parts of desalted water, SAPO 1
Part, 2.5~4 parts of clay, 0.4~0.9 part of silicon source, 0.7~1.2 part of silicon source and 0.01~0.1 part of diluted acid, are mixed into slurry
Liquid, wherein SAPO are a kind of molecular screen primary powders；
Second step：Slurries are delivered in shaping tower through centrifugal pump and carry out mist projection granulating shaping；
3rd step：The communicated band of material after shaping is delivered to fill and is stirred in the exchange kettle for exchanging liquid, is obtained
The material of metal is loaded with, exchange liquid is the one or several kinds in platinum nitrate, rhodium nitrate, palladium nitrate；
4th step：The slurries that exchange is finished are delivered to progress filtering means dehydration operation on vacuum belt filter；
5th step：Material after being dehydrated through vacuum belt filter is collected in collector, is then placed in industrial furnace and is dried
Roasting, that is, obtain the sial phosphorus molecular sieve of carried metal；
6th step：Sealing pack is carried out to the sial phosphorus molecular sieve of the carried metal after drying roasting.
It is preferred that, the desalted water, SAPO, clay, silicon source, silicon source, the quality parts ratio of diluted acid are 11~23：1：3.1
~4：0.4~0.8：0.8~1.1：0.01~0.08.
It is preferred that, the mass concentration for exchanging liquid is 0.05~2%.
It is preferred that, the clay is the one or several kinds in kaolin, bentonite, ball clay, fire clay.
It is preferred that, the silicon source is model JN-20, JN-25, JN-30, JN-40, SW- of Ludox, wherein Ludox
20th, the one or more in SW-25, SW-30.
It is preferred that, source of aluminium is boehmite, and diluted acid is the one or more in watery hydrochloric acid, dust technology, dilute sulfuric acid.
It is preferred that, it is 6.0~7.0 that the electrical conductivity of the desalted water, which is less than 5 μ S/cm, pH,.
It is preferred that, the forming process is completed in shaping tower, and the upper strata temperature of shaping tower is 150~230 DEG C, lower floor's temperature
Spend for 100~150 DEG C, a diameter of 1~2mm of shower nozzle.
It is preferred that, the program that roasting is dried in the industrial furnace is as follows：
(1) normal temperature is raised to 120~150 DEG C, keeps 6~8h；
(2) 400~500 DEG C are continuously heating to, 1~2h is kept；
(3) 600~800 DEG C are continuously heating to, 6~10h is kept；
(4) wind cooling temperature lowering.
Present invention also offers the application of the sial phosphorus molecular sieve of carried metal, by the sial phosphorus molecular sieve of carried metal with
It is (0.05~1) that sial phosphorus molecular sieve made from the 3rd step is not carried out according to mass ratio:1 is placed in alcohol ether olefine reaction regeneration system
In system, reaction regeneration operation is carried out, the CO gases for promoting to produce in regenerator are converted into CO2, alcohol ether reaction regenerative system
The temperature of middle reactor is 400-490 DEG C, and the temperature of regenerator is 600-650 DEG C, and reactor pressure is 1.5-2.5Mpa, then
Pressure is 0.3-1.5MPa in raw device.
Relative to prior art, the sial phosphorus molecular sieve of carried metal of the present invention and application have the advantage that：
The sial phosphorus molecular sieve of carried metal of the present invention and application, are exchanged in liquid by the way that molecular sieve is entered, will
Metallic element loads the sial phosphorus molecular sieve for forming carried metal over a molecular sieve, should by the sial phosphorus molecular sieve of carried metal
Reaction regeneration operation is carried out for alcohol ether olefine reaction regenerative system, promotes the CO gases produced in regenerator to be converted into CO2,
The CO contents in regenerator are made to be reduced to 1.5% or lower by 3~7%, at the same time can in the conversion process that CO occurs
To discharge substantial amounts of heat, the supplement to heat in regenerator is saved, the carbon distribution effect on molecular sieve catalyst had so both been eliminated
Should, recover the activity of molecular sieve catalyst, pollutions of the CO to environment is eliminated again, the consumption of the energy has been saved, while to big
Compression ring border is also made that contribution, and environmental protection of the present invention, good energy-conserving effect, automaticity is high, is easy to industrialization promotion.
Brief description of the drawings
Fig. 1 is the preparation technology figure of the sial phosphorus molecular sieve of carried metal；
Fig. 2 is the energy spectrum diagram of the sial phosphorus molecular sieve of carried metal.
Description of reference numerals：
1- batching kettles；2- is molded tower；3- exchanges kettle；4- vacuum belt filters；5- collectors.
Embodiment
In addition to being defined, technical term used has universal with those skilled in the art of the invention in following examples
The identical meanings of understanding.Test reagent used, is routine biochemistry reagent unless otherwise specified in following examples；It is described
Experimental method, is conventional method unless otherwise specified.
The present invention is described in detail with reference to embodiment and accompanying drawing.
Comparative example
It is 6.3 15 parts of desalted water, 1 part of SAPO-34, kaolinite that electrical conductivity 4 μ S/cm, pH is sequentially added in batching kettle 1
0.04 part of 2.7 parts of soil, 0.8 part of Ludox, 1 part of boehmite and nitric acid, are mixed into slurries；Slurries are defeated through centrifugal pump
Deliver to and mist projection granulating shaping is carried out in shaping tower 2, the upper strata temperature of shaping tower 2 is 190 DEG C, and lower floor's temperature is 120 DEG C, shower nozzle
A diameter of 1.8mm；It is then placed in industrial furnace and dries roasting, the program that roasting is dried in industrial furnace is：(1) normal temperature is raised to
130 DEG C, keep 6h；(2) 420 DEG C are continuously heating to, 1h is kept；(3) 680 DEG C are continuously heating to, 8h is kept；(4) wind cooling temperature lowering.
Obtain the sial phosphorus molecular sieve of carried metal；Sealing dress is carried out to the sial phosphorus molecular sieve of the carried metal after drying roasting.
Sial phosphorus molecular sieve made from the above method is placed in alcohol ether olefine reaction regenerative system and carries out reaction regeneration operation, wherein instead
It is 450 DEG C to answer device, and regenerator is 610 DEG C, and reactor pressure is that pressure is 0.8MPa in 1.8Mpa, regenerator, in regenerator
CO and CO2Content is drawn through gas chromatographic analysis.
Embodiment 1
It is 6.8 23 parts of desalted water, 1 part of SAPO-34, kaolinite that electrical conductivity 3 μ S/cm, pH is sequentially added in batching kettle 1
0.01 part of 3.1 parts of soil, 0.5 part of Ludox, 0.8 part of boehmite and hydrochloric acid, are mixed into slurries；By slurries through centrifugal pump
It is delivered in shaping tower 2 and carries out mist projection granulating shaping, the upper strata temperature of shaping tower 2 is 180 DEG C, and lower floor's temperature is 120 DEG C, shower nozzle
A diameter of 1.4mm；The communicated band of material after shaping is delivered in the exchange kettle 3 for fill platinum nitrate solution and is stirred,
Wherein the mass concentration of platinum nitrate is 2.1%, and the volume of platinum nitrate solution is 100 times of the quality of the above-mentioned molecular sieve added,
Obtain being loaded with the material of metal, the slurries that exchange is finished are delivered to progress filtering means dehydration operation on vacuum belt filter 4；Through true
Material after the dehydration of blanking bar filter is collected in collector 5, is then placed in industrial furnace and is dried roasting, is dried in industrial furnace
The program of roasting is：(1) normal temperature is raised to 150 DEG C, keeps 7h；(2) 450 DEG C are continuously heating to, 2h is kept；(3) it is continuously heating to
680 DEG C, keep 8h；(4) wind cooling temperature lowering.Obtain the sial phosphorus molecular sieve of carried metal；To the carried metal after drying roasting
Sial phosphorus molecular sieve carry out sealing dress.
The metal of load is 0.024g, by the above-mentioned sial phosphorus molecular sieve for having loaded metal with not carrying out made from the 3rd step
Sial phosphorus molecular sieve is 1 according to mass ratio:20, alcohol ether olefine reaction regenerative system is placed in after being well mixed and carries out reaction regeneration
Operation, wherein reactor is 450 DEG C, and regenerator is 610 DEG C, and reactor pressure is that pressure is in 1.8Mpa, regenerator
CO and CO in 0.8MPa, wherein regenerator2Content is drawn through gas chromatographic analysis.
Energy spectrum analysis is carried out to the sial phosphorus molecular sieve of carried metal：
As can see from Figure 2 metal platinum has been loaded on the sial phosphorus molecular sieve of carried metal.
Embodiment 2
It is 7.0 11 parts of desalted water, 1 part of SAPO-34, kaolinite that electrical conductivity 2 μ S/cm, pH is sequentially added in batching kettle 1
0.08 part of 3.1 parts of soil, 0.8 part of Ludox, 0.8 part of boehmite and sulfuric acid, are mixed into slurries；By slurries through centrifugal pump
It is delivered in shaping tower 2 and carries out mist projection granulating shaping, the upper strata temperature of shaping tower 2 is 220 DEG C, and lower floor's temperature is 110 DEG C, shower nozzle
A diameter of 2mm；The communicated band of material after shaping is delivered in the exchange kettle 3 for fill platinum nitrate solution and is stirred, its
The mass concentration of middle platinum nitrate is 1.7%, and the volume of platinum nitrate solution is 80 times of the quality of the above-mentioned molecular sieve of addition, is obtained
The material of metal is loaded with, the slurries that exchange is finished are delivered to progress filtering means dehydration operation on vacuum belt filter 4；Through vacuum belt
Material after filter 4 is dehydrated is collected in collector 5, is then placed in industrial furnace and is dried roasting, and roasting is dried in industrial furnace
The program of burning is：(1) normal temperature is raised to 140 DEG C, keeps 8h；(2) 400 DEG C are continuously heating to, 2h is kept；(3) 800 are continuously heating to
DEG C, keep 10h；(4) wind cooling temperature lowering.Obtain the sial phosphorus molecular sieve of carried metal；To the carried metal after drying roasting
Sial phosphorus molecular sieve carries out sealing dress.
The metal of load is 0.011g, by the above-mentioned sial phosphorus molecular sieve for having loaded metal with not carrying out made from the 3rd step
Sial phosphorus molecular sieve is 1 according to mass ratio:45, alcohol ether olefine reaction regenerative system is placed in after being well mixed and carries out reaction regeneration
Operation, wherein reactor is 450 DEG C, and regenerator is 610 DEG C, and reactor pressure is that pressure is in 1.8Mpa, regenerator
CO and CO in 0.8MPa, wherein regenerator2Content is drawn through gas chromatographic analysis.
Embodiment 3
It is 6.2 20 parts of desalted water, 1 part of SAPO-34, kaolinite that electrical conductivity 3 μ S/cm, pH is sequentially added in batching kettle 1
0.05 part of 4 parts of soil, 0.4 part of Ludox, 1.1 parts of boehmite and nitric acid, are mixed into slurries；Slurries are defeated through centrifugal pump
Deliver to and mist projection granulating shaping is carried out in shaping tower 2, the upper strata temperature of shaping tower 2 is 230 DEG C, and lower floor's temperature is 110 DEG C, shower nozzle
A diameter of 1.1mm；The communicated band of material after shaping is delivered in the exchange kettle 3 for fill platinum nitrate solution and is stirred, its
The mass concentration of middle platinum nitrate is 1.9%, and the volume of platinum nitrate solution is 82 times of the quality of the above-mentioned molecular sieve of addition, is obtained
The material of metal is loaded with, the slurries that exchange is finished are delivered on vacuum belt filter, 4 and carry out filtering means dehydration operation；Through vacuum belt
Material after filter 4 is dehydrated is collected in collector 5, is then placed in industrial furnace and is dried roasting, and roasting is dried in industrial furnace
The program of burning is：(1) normal temperature is raised to 120 DEG C, keeps 6h；(2) 500 DEG C are continuously heating to, 1.7h is kept；(3) it is continuously heating to
690 DEG C, keep 8h；(4) wind cooling temperature lowering.Obtain the sial phosphorus molecular sieve of carried metal；To the carried metal after drying roasting
Sial phosphorus molecular sieve carry out sealing dress.
The metal of load is 0.021g, by the above-mentioned sial phosphorus molecular sieve for having loaded metal with not carrying out made from the 3rd step
Sial phosphorus molecular sieve is 1 according to mass ratio:89, alcohol ether olefine reaction regenerative system is placed in after being well mixed and carries out reaction regeneration
Operation, wherein reactor is 450 DEG C, and regenerator is 610 DEG C, and reactor pressure is that pressure is in 1.8Mpa, regenerator
CO and CO in 0.8MPa, wherein regenerator2Content is drawn through gas chromatographic analysis.
The experimental result of comparative example and embodiment 1,2,3：Growing amount accounts for the volume integral of the angry body of total yield per hour by CO and CO2
Number.
As can be seen from the above table, the volume content of the CO in the regenerator for the sial phosphorus molecular sieve that with the addition of carried metal subtracts
CO that is small, changing into2Volume content increase, the addition of the sial phosphorus molecular sieve of carried metal effectively facilitated CO and changed into
CO2。
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
God is with principle, and any modification, equivalent substitution and improvements made etc. should be included in the scope of the protection.
Claims (10)
1. a kind of sial phosphorus molecular sieve of carried metal, it is characterised in that：It is prepared from by following steps：
The first step：Sequentially add the component of following quality parts ratio：10~24 parts of desalted water, 1 part of SAPO, 2.5~4 parts of clay,
0.01~0.1 part of 0.4~0.9 part of silicon source, 0.7~1.2 part of silicon source and diluted acid, are mixed into slurries；
Second step：Slurries are subjected to mist projection granulating shaping after centrifugation；
3rd step：Material after shaping is stirred with exchanging liquid, obtains being loaded with the material of metal, exchange liquid is nitric acid
One or several kinds in platinum, rhodium nitrate, palladium nitrate；
4th step：The slurries progress filtering means dehydration operation finished will be exchanged；
5th step：Material after dehydration is then placed in industrial furnace through collecting and dries roasting, that is, obtain the silicon of carried metal
Aluminium phosphorus molecular sieve；
6th step：Sealing pack is carried out to the sial phosphorus molecular sieve of the carried metal after drying roasting.
2. the sial phosphorus molecular sieve of carried metal according to claim 1, it is characterised in that：It is the desalted water, SAPO, glutinous
Soil, silicon source, silicon source, the quality parts ratio of diluted acid are 11~23 parts：1 part：3.1~4 parts：0.4~0.8 part：0.8~1.1 part：
0.01~0.08 part.
3. the sial phosphorus molecular sieve of carried metal according to claim 1, it is characterised in that：The quality for exchanging liquid is dense
Spend for 0.05~2%.
4. the sial phosphorus molecular sieve of carried metal according to claim 1, it is characterised in that：The clay be kaolin,
One or several kinds in bentonite, ball clay, fire clay.
5. the sial phosphorus molecular sieve of carried metal according to claim 1, it is characterised in that：The silicon source is Ludox,
One or more wherein in model JN-20, JN-25, JN-30, JN-40, SW-20, SW-25, SW-30 of Ludox.
6. the sial phosphorus molecular sieve of carried metal according to claim 1, it is characterised in that：Source of aluminium is the thin water aluminium of plan
Stone, diluted acid is the one or more in watery hydrochloric acid, dust technology, dilute sulfuric acid.
7. the sial phosphorus molecular sieve of carried metal according to claim 1, it is characterised in that：The electrical conductivity of the desalted water
It is 6.0~7.0 less than 5 μ S/cm, pH.
8. the sial phosphorus molecular sieve of carried metal according to claim 1, it is characterised in that：Forming process is in shaping tower
Complete, the upper strata temperature of shaping tower is 150~230 DEG C, and lower floor's temperature is 100~150 DEG C, a diameter of 1~2mm of shower nozzle.
9. the sial phosphorus molecular sieve of carried metal according to claim 1, it is characterised in that：Dried in the industrial furnace
The program of roasting is as follows：
(1) normal temperature is raised to 120~150 DEG C, keeps 6-8h；
(2) 400~500 DEG C are continuously heating to, 1-2h is kept；
(3) 600~800 DEG C are continuously heating to, 6-10h is kept；
(4) wind cooling temperature lowering.
10. a kind of application of the sial phosphorus molecular sieve of carried metal as described in any one of claim 1~9, it is characterised in that：
By the sial phosphorus molecular sieve of carried metal and do not carry out sial phosphorus molecular sieve made from the 3rd step according to mass ratio for (0.05~
1)：1 is placed in alcohol ether olefine reaction regenerative system, reaction regeneration operation is carried out, for the CO gas for promoting to produce in regenerator
Body is converted into CO2, the temperature of reactor is 400-490 DEG C wherein in alcohol ether reaction regenerative system, and the temperature of regenerator is 600-
650 DEG C, reactor pressure is that pressure is 0.3-1.5MPa in 1.5-2.5Mpa, regenerator.
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| CN108545759A (en) * | 2018-04-18 | 2018-09-18 | 中国天辰工程有限公司 | A kind of preparation method and its evaluating apparatus of the sial phosphorus molecular sieve of modification |
| CN109650404A (en) * | 2018-12-20 | 2019-04-19 | 中国天辰工程有限公司 | A kind of solid sial phosphorus molecular sieve forming method and device |
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| CN109650404A (en) * | 2018-12-20 | 2019-04-19 | 中国天辰工程有限公司 | A kind of solid sial phosphorus molecular sieve forming method and device |
| CN109650404B (en) * | 2018-12-20 | 2020-12-15 | 中国天辰工程有限公司 | Method and device for forming solid silicon-aluminum-phosphorus molecular sieve |
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