CN111229292A - Preparation method of shape-selective isomerization catalyst based on FAU-type structure molecular sieve - Google Patents
Preparation method of shape-selective isomerization catalyst based on FAU-type structure molecular sieve Download PDFInfo
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 100
- 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 100
- 239000003054 catalyst Substances 0.000 title claims abstract description 74
- 238000006317 isomerization reaction Methods 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000011148 porous material Substances 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 32
- 239000012298 atmosphere Substances 0.000 claims abstract description 31
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 22
- 239000007789 gas Substances 0.000 claims abstract description 14
- 239000000843 powder Substances 0.000 claims abstract description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 13
- 239000001301 oxygen Substances 0.000 claims abstract description 13
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 12
- 238000011068 loading method Methods 0.000 claims abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 49
- 229910052799 carbon Inorganic materials 0.000 claims description 48
- 238000000151 deposition Methods 0.000 claims description 32
- 230000008021 deposition Effects 0.000 claims description 32
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 229910052697 platinum Inorganic materials 0.000 claims description 8
- 230000009467 reduction Effects 0.000 claims description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 238000011049 filling Methods 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 4
- 229910052793 cadmium Inorganic materials 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 150000003983 crown ethers Chemical class 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 238000004729 solvothermal method Methods 0.000 claims description 2
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- 230000001276 controlling effect Effects 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 6
- 239000012188 paraffin wax Substances 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 238000012512 characterization method Methods 0.000 description 7
- 238000006555 catalytic reaction Methods 0.000 description 6
- 238000009792 diffusion process Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000010453 quartz Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000005336 cracking Methods 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 239000003502 gasoline Substances 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000010687 lubricating oil Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229940094933 n-dodecane Drugs 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000004904 shortening Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical class N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- 238000005985 Hofmann elimination reaction Methods 0.000 description 1
- KMWBBMXGHHLDKL-UHFFFAOYSA-N [AlH3].[Si] Chemical compound [AlH3].[Si] KMWBBMXGHHLDKL-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- 239000002199 base oil Substances 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000004375 physisorption Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000000352 supercritical drying Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000009489 vacuum treatment Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
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- 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
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
- B01J29/12—Noble metals
- B01J29/126—Y-type faujasite
-
- 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
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
- B01J29/14—Iron group metals or copper
- B01J29/146—Y-type faujasite
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
-
- 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
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a preparation method of an isomerization catalyst taking an FAU-type structure molecular sieve as a carrier. The preparation method of the catalyst comprises the following specific steps: firstly, roasting molecular sieve raw powder containing a template agent and having an FAU-type structure in an oxygen-containing atmosphere or an inert atmosphere at the temperature of 200-450 ℃; then loading the VIII group noble metal active component on the treated molecular sieve, and drying and reducing to obtain the target catalyst. The depth of the molecular sieve pore channel is regulated and controlled by controlling the roasting atmosphere and temperature in the molecular sieve carrier and the flow velocity of the reducing gas. Compared with the catalyst prepared by the prior art, the catalyst prepared by the method of the invention has high reaction activity and isomer yield in the normal paraffin isomerization reaction.
Description
Technical Field
The invention belongs to the fields of petrochemical industry, fine chemical industry and molecular sieve catalysts, and particularly relates to a preparation method and application of a shape-selective isomerization catalyst taking an FAU-type structure molecular sieve as a carrier.
Technical Field
The alkane isomerization reaction plays an important role in the quality improvement process of oil products. The hydroisomerization of light paraffins can produce gasoline blending components of high octane number, while the hydroisomerization of long-chain paraffins is mainly used to improve the low-temperature flow properties of aviation kerosene, diesel fuel and lubricating oils. At present, the most advanced catalyst applied to the reaction is a bifunctional catalyst taking a molecular sieve as a carrier and loading a metal component with a (de) hydrogenation performance. The preparation of catalysts for isomerization of alkanes using molecular sieves as carriers is reported in patent documents US4710485, 5135638, 5282598, CN1792451, 1788844, 101245260, etc.
In the isomerization reaction of the alkane, the pore channel structure of the molecular sieve has the shape-selective function and simultaneously has the diffusion problem. The diffusion type of alkane molecules in the molecular sieve belongs to configuration diffusion, and the diffusion capability is poor; and because the length of the pore channel of the molecular sieve is usually much longer than that of alkane molecules, the diffusion time of the alkane molecules in the molecular sieve is long. In addition, acid centers in the pores of the molecular sieve catalyze the cracking reaction of monomethyl intermediates in the pores of the molecular sieve. Diffusion problems and cracking reactions within the channels will result in a reduction of the catalyst reactivity and isomer selectivity. Isomerization of long chain n-alkanes over molecular sieve catalysts follows a pore and lock and key shape selective mechanism. According to this mechanism, the hydroisomerization of linear paraffins takes place predominantly at the pore openings of the molecular sieve pores, which means that the reactivity and shape-selective function of the molecular sieve catalyst are determined predominantly by the nature of the acid and the steric environment in the vicinity of the pore openings of the molecular sieve. In conclusion, the preparation of the isomerization catalyst with high activity and high selectivity can be realized by shortening the depth of the molecular sieve pore channel and reducing the acid amount and the acid strength in the pore channel while keeping the pore opening of the molecular sieve.
In the preparation of molecular sieve catalysts, the template agent in the molecular sieve is usually removed by high-temperature (not lower than 450 ℃) roasting to obtain a smooth pore structure. Generally, the synthesis of the molecular sieve takes organic amine as a template agent, and the roasting removal of the organic amine mainly comprises two stages: the organic amine mainly generates Hofmann elimination decomposition reaction in the low-temperature stage, and the organic amine and carbon-containing species mainly generate oxidation combustion in the high-temperature stage. The combustion process consumes a large amount of oxygen and generates a large amount of heat, which can result in incomplete combustion and pyrolysis of the template to produce carbon deposits. By selecting proper calcination temperature and duration, the carbon deposit can be retained, and the molecular sieve pore channels are partially filled, so that the purposes of shortening the depth of the channel, reducing the number of acid centers in the pore channels and simultaneously retaining the pore openings are achieved.
Y, Me-Y (Me is Zn, Mg, Mn, Co, Cr, Cu, Fe, Cd or Ni) molecular sieve is a kind of artificially synthesized silicon-aluminium microporous molecular sieve, belonging to FAU topological structure and having three-dimensional twelve-membered ring channel structure and orifice size of about
The supported catalyst taking the supported catalyst as the carrier shows excellent performance in the hydroisomerization reaction of long-chain alkane. Similar to the molecular sieve demoulding means, the preparation of the catalyst taking the FAU type molecular sieve as the carrier usually adopts high-temperature (not lower than 450 ℃) roasting to remove the template agent in the molecular sieve, so as to prepare the molecular sieve carrier with completely unobstructed microporous pore passages of the molecular sieve. In practical use, the transparent and long and narrow microporous pore channels tend to reduce the activity of the catalyst and the selectivity of isomers.
Therefore, the invention provides a preparation method of a shape selective isomerization catalyst taking an FAU-type structure molecular sieve as a carrier. Using molecular sieve raw powder containing a template agent and having an FAU-shaped structure, and carrying out low-temperature roasting treatment in an oxygen-containing atmosphere or an inert atmosphere to carbonize the template agent to form carbon deposition which partially fills microporous pore channels of the molecular sieve; and then loading a metal active component on the obtained molecular sieve carrier, and drying and reducing at low temperature to obtain the target catalyst. By controlling the roasting atmosphere and temperature, the reduction temperature and the flow velocity of the reduction gas, the in-situ generation of carbon deposition in the molecular sieve pore channels is realized, and the depth of the molecular sieve pore channels is effectively regulated and controlled. Compared with the catalyst prepared by the prior art, the catalyst prepared by the method has higher activity and isomer yield in the normal paraffin isomerization reaction.
Disclosure of Invention
The invention aims to provide a preparation method of an isomerization catalyst taking an FAU-type structure molecular sieve as a carrier.
Specifically, the invention provides a preparation method of an isomerization catalyst taking an FAU-type structure molecular sieve as a carrier, which is characterized by comprising the following steps: roasting the molecular sieve with the FAU type structure at low temperature in an oxygen-containing atmosphere or an inert atmosphere to convert a template agent contained in the molecular sieve into carbon deposit, partially filling the carbon deposit into microporous pore channels of the molecular sieve, then loading a metal component, and continuously maintaining the carbon deposit in the micropores of the molecular sieve through drying and reduction to prepare the shape-selective isomerization catalyst, which comprises the following steps:
(1) roasting molecular sieve raw powder containing a template agent and having an FAU-type structure for 0.5-24h at the temperature of 200-450 ℃ in an oxygen-containing atmosphere or an inert atmosphere, converting the template agent contained in the molecular sieve raw powder into carbon deposition and filling the carbon deposition in a molecular sieve pore channel,
(2) loading the calcined molecular sieve in the step (1) with a VIII group noble metal active component, wherein the content of the VIII group noble metal component is 0.05-10 wt.%,
(3) the sample loaded with the VIII group noble metal component in the step (2) is put in a reducing atmosphere at the temperature of 150 ℃ and 450 ℃ and the flow rate of reducing gas is 1-50mL/min/gCatalyst and process for preparing sameAnd reducing for 0.5-12h to continuously maintain carbon deposition in the molecular sieve, thereby preparing the shape selective isomerization catalyst.
The molecular sieve with the FAU-type structure in the step (1) of the method provided by the invention is one or more of Y, Me-Y (Me ═ Zn, Mg, Mn, Co, Cr, Cu, Fe, Cd or Ni and the like), SAPO-37 and the like;
the molecular sieve raw powder in the step (1) of the method is a molecular sieve which is synthesized according to a conventional hydrothermal method or a solvothermal method, washed and dried and is not subjected to template agent removal treatment; the template agent is one or more of crown ether, tetrapropylammonium hydroxide, tetramethylammonium hydroxide and the like, and the content of the template agent is 0.5-20 wt.% of the weight of the molecular sieve.
The oxygen-containing atmosphere in the step (1) of the method provided by the invention is oxygen or a mixed gas of oxygen and other gases; the inert atmosphere is one or more of nitrogen, helium and argon.
The treatment temperature in the step (1) of the method provided by the invention is 250-400 ℃, and the treatment time is 1-12 h.
In the method provided by the invention, the active component of the VIII group noble metal in the step (2) or the step (3) is one or more of elements such as Pt, Pd, Ir and the like, and the content of the VIII group noble metal is 0.05-5.0 wt.%.
The reducing atmosphere in the step (3) of the method provided by the invention is hydrogen or the mixed gas of hydrogen and other gases (such as inert gas, alkane, alkene and the like), and the flow rate of the reducing gas is 5-40mL/min/gCatalyst and process for preparing same。
The reduction temperature in the step (3) of the method provided by the invention is 200-.
In the method provided by the invention, the carbon content in the microporous pore channel of the shape selective isomerization catalyst is 0.5-16 wt% of the weight of the catalyst.
The loading of the metal component in the step (2) of the method provided by the invention adopts operation methods conventional in the art, including but not limited to impregnation, precipitation, deposition, adhesive bonding or mechanical pressing, etc., so that the group VIII noble metal precursor is dispersed on the carrier to realize the combination of the group VIII noble metal and the carrier; the metal precursors used include, but are not limited to, metal acids, metal acid salts, chlorides, ammonia complexes, carbonyl complexes, or mixtures thereof;
the metal component is loaded on the treated molecular sieve in the step (2) of the method provided by the invention and then needs to be dried by adopting the conventional operation methods in the field, including but not limited to heating drying, freeze drying, supercritical drying and the like, and the common method is to carry out drying at 40-300 ℃ in an air atmosphere, preferably at 60-200 ℃; drying for 0.5-24h, preferably for 1-8 h;
the catalyst provided by the invention can be widely applied to the processing processes of petroleum fractions, biomasses and Fischer-Tropsch synthesis products, such as the processes of isomerization pour point depression, isomerization dewaxing and the like.
Compared with the conventional preparation method, the preparation method of the shape selective isomerization catalyst taking the FAU-type structure molecular sieve as the carrier has the following advantages:
1. the roasting and demolding temperature of the molecular sieve carrier is reduced, and the energy consumption in the preparation process of the catalyst is reduced;
2. the carbon deposition generated in situ in the preparation process partially fills the microporous pore canal of the molecular sieve, shortens the depth of the pore canal, shortens the length of the carbon chain of the adsorbate inserted into the microporous pore canal, and obviously improves the mass transfer of reactants and intermediate products;
3. the prepared selective isomerization catalyst has higher activity and isomer yield, particularly the yield of multi-branched isomer in the isomerization reaction of the alkane; the method is applied to the processing process of petroleum fractions, biomasses and Fischer-Tropsch synthesis products, and can obviously improve the product yield and the product performance, such as the octane number of a gasoline product, the cetane number of a diesel product, the pour point of a lubricating oil base oil product and the like.
Detailed Description
The present invention will be further illustrated by the following examples, but the present invention is not limited to the following examples. Meanwhile, the embodiments only give some conditions for achieving the purpose, and do not mean that the conditions must be met for achieving the purpose.
And determining the carbon deposition content of the sample according to the thermogravimetric analysis result. The samples were subjected to thermogravimetric measurements using an instrument of type STA 449F 3, NETZSCH company, germany. The measurement conditions were as follows: the sample loading was 20mg and the temperature was raised from 40 ℃ to 900 ℃ at a rate of 10 ℃/min in an air atmosphere (flow 20 ml/min). The carbon deposition content of the sample is the weight loss of more than 300 ℃ in the thermogravimetric result of the sample.
Pore volume measurements of the catalysts were performed on a Micromeritics ASAP2420 physisorption instrument. Before testing, the samples were subjected to a vacuum treatment at 200 ℃ for 6h and then to N at liquid nitrogen temperature2And (4) measuring adsorption and desorption isotherms. The micropore volume of the sample was calculated by the t-plot method.
The catalyst evaluation is carried out in a stainless steel fixed bed reactor, and 1.0mL of the prepared catalyst is loaded in a reactionIn the reactor, the temperature is raised to the reaction temperature under the hydrogen atmosphere, raw oil n-dodecane is reacted, and the product is analyzed by gas chromatography. Reaction conditions are as follows: the reaction temperature is 200 ℃ and 300 ℃, the normal pressure is realized, and the hourly space velocity of n-dodecane liquid is 1.0h-1The hydrogen-oil ratio (mol/mol) was 15.
Comparative example
20g of template-containing Y molecular sieve raw powder is placed in a quartz tube, roasted for 24h at 560 ℃ in air atmosphere, and naturally cooled to room temperature to obtain a Y molecular sieve carrier with smooth pore channels, wherein the content of carbon deposition in the molecular sieve carrier is 0, and the pore volume of micropores is 0.208cm3(ii) in terms of/g. With 5.0mL of H containing 0.001g/mL of Pt2PtCl6The solution was impregnated with 5g of the above molecular sieve support. The impregnated sample was dried at 120 ℃ for 2h and reduced at 500 ℃ for 4h in a hydrogen atmosphere to give 0.5 wt.% Pt/Y catalyst. The carbon content in the catalyst is 0, and the micropore volume is 0.208cm3(ii) in terms of/g. The carbon deposition content and micropore volume characterization results of the catalyst are shown in table 1, and the catalytic reaction evaluation results are shown in table 2.
Example 1
20g of template-containing Y molecular sieve raw powder is placed in a quartz tube, roasted for 4h at 250 ℃ in the air atmosphere, and naturally cooled to room temperature to obtain a Y molecular sieve carrier with microporous channels partially filled with carbon deposition, wherein the carbon deposition content in the molecular sieve carrier is 12.3 percent, and the microporous pore volume is 0.016cm3(ii) in terms of/g. With 5.0mL of H containing 0.001g/mL of Pt2PtCl6The solution was impregnated with 5g of the above molecular sieve support. Drying the impregnated sample at 120 deg.C for 2h, and controlling hydrogen flow rate at 200 deg.C to 5mL/min/gCatalyst and process for preparing sameReduction for 4h, yielding 0.5 wt.% Pt/Y catalyst. The carbon content in the catalyst is 12.3 percent, and the micropore volume is 0.016cm3(ii) in terms of/g. The carbon deposition content and micropore volume characterization results of the catalyst are shown in table 1, and the catalytic reaction evaluation results are shown in table 2.
Example 2
20g of template-containing Y molecular sieve raw powder is placed in a quartz tube, roasted for 4h at 320 ℃ in nitrogen atmosphere, and naturally cooled to room temperature to obtain a Y molecular sieve carrier with microporous channels partially filled with carbon deposition, wherein the carbon deposition content in the molecular sieve carrier is 7.3%, and the microporous pore volume is 0.064cm3(ii) in terms of/g. With 5.0mL of H containing 0.001g/mL of Pt2PtCl6The solution was impregnated with 5g of the above molecular sieve support. Drying the impregnated sample at 120 deg.C for 2h, and controlling hydrogen flow rate at 300 deg.C to 20mL/min/gCatalyst and process for preparing sameReduction for 4h, yielding 0.5 wt.% Pt/Y catalyst. The carbon content in the catalyst is 7.3 percent, and the micropore volume is 0.064cm3(ii) in terms of/g. The carbon deposition content and micropore volume characterization results of the catalyst are shown in table 1, and the catalytic reaction evaluation results are shown in table 2.
Example 3
20g of template-containing Y molecular sieve raw powder is placed in a quartz tube, roasted for 4h at 400 ℃ in air atmosphere, and naturally cooled to room temperature to obtain a Y molecular sieve carrier with microporous channels partially filled with carbon deposition, wherein the carbon deposition content in the molecular sieve carrier is 1.4%, and the microporous pore volume is 0.183cm3(ii) in terms of/g. With 5.0mL of H containing 0.001g/mL of Pt2PtCl6The solution was impregnated with 5g of the above molecular sieve support. Drying the impregnated sample at 120 deg.C for 2h, and controlling hydrogen flow rate at 400 deg.C to 40mL/min/gCatalyst and process for preparing sameReduction for 4h, yielding 0.5 wt.% Pt/Y catalyst. The carbon content in the catalyst is 1.2 percent, and the micropore volume is 0.189cm3(ii) in terms of/g. The carbon deposition content and micropore volume characterization results of the catalyst are shown in table 1, and the catalytic reaction evaluation results are shown in table 2.
Example 4
20g of SnY molecular sieve raw powder containing a template agent is placed in a quartz tube, roasted for 12h at 350 ℃ in air atmosphere, and naturally cooled to room temperature to obtain a Y molecular sieve carrier with microporous channels partially filled with carbon deposition, wherein the carbon deposition content in the molecular sieve carrier is 5.7 percent, and the microporous pore volume is 0.085cm3(ii) in terms of/g. With 5.0mL of H containing 0.001g/mL of Pt2PtCl6The solution was impregnated with 5g of the above molecular sieve support. Drying the impregnated sample at 120 deg.C for 2h, and controlling hydrogen flow rate at 300 deg.C to 10mL/min/gCatalyst and process for preparing sameReduction for 4h, yielding 0.5 wt.% Pt/Y catalyst. The carbon content in the catalyst is 5.7 percent, and the micropore volume is 0.085cm3(ii) in terms of/g. The carbon deposition content and micropore volume characterization results of the catalyst are shown in table 1, and the catalytic reaction evaluation results are shown in table 2.
Example 5
20g of FeY molecular sieve raw powder containing a template agent is placed in a quartz tube and is subjected to air atmosphereRoasting at 280 ℃ for 4h, naturally cooling to room temperature to obtain the Y molecular sieve carrier with the microporous pore channels partially filled with carbon deposition, wherein the carbon deposition content in the molecular sieve carrier is 9.4%, and the microporous pore volume is 0.038cm3(ii) in terms of/g. With 5.0mL of H containing 0.001g/mL of Pt2PtCl6The solution was impregnated with 5g of the above molecular sieve support. Drying the impregnated sample at 120 deg.C for 2h, and controlling hydrogen flow rate at 300 deg.C to 20mL/min/gCatalyst and process for preparing sameReduction for 4h, yielding 0.5 wt.% Pt/Y catalyst. The carbon content in the catalyst is 8.4 percent, and the micropore volume is 0.045cm3(ii) in terms of/g. The carbon deposition content and micropore volume characterization results of the catalyst are shown in table 1, and the catalytic reaction evaluation results are shown in table 2.
TABLE 1 characterization results of catalysts in comparative examples and examples
TABLE 2 evaluation results of catalysts in comparative examples and examples
As can be seen from Table 1, in the comparative example, the template agent was completely removed by a conventional method, the carbon deposition content of the FAU-structured molecular sieve support (Y) was 0, and the microporous pore passage was completely unobstructed. In examples 1 to 5, the molecular sieve support (Y and MeY) having an FAU structure obtained by the method for converting a template agent into carbon deposition according to the present invention contained carbon deposition, and had a reduced pore volume of the molecular sieve, and filled a part of the microporous channels, so that the depth of the microporous channels was shortened.
As can be seen from Table 2, the catalysts obtained in examples 1 to 5 using the present process can obtain higher activity and isomer yield, particularly multi-branched isomer yield, in the hydroisomerization reaction of paraffins, as compared with the catalysts obtained in the conventional process of comparative example.
Claims (9)
1. A preparation method of a shape selective isomerization catalyst taking an FAU-type structure molecular sieve as a carrier is characterized by comprising the following steps: roasting the molecular sieve with the FAU type structure at low temperature in an oxygen-containing atmosphere or an inert atmosphere to convert a template agent contained in the molecular sieve into carbon deposit, partially filling the carbon deposit into microporous pore channels of the molecular sieve, then loading a metal component, and continuously maintaining the carbon deposit in the micropores of the molecular sieve through drying and reduction to prepare the shape-selective isomerization catalyst, which comprises the following steps:
(1) roasting molecular sieve raw powder containing a template agent and having an FAU-type structure for 0.5-24h at the temperature of 200-450 ℃ in an oxygen-containing atmosphere or an inert atmosphere, converting the template agent contained in the molecular sieve raw powder into carbon deposition and filling the carbon deposition in a molecular sieve pore channel,
(2) loading the molecular sieve calcined in the step (1) with a VIII group noble metal active component, wherein the content of the VIII group noble metal component is 0.05-10 wt.%,
(3) the sample loaded with the VIII group noble metal component in the step (2) is put in a reducing atmosphere at the temperature of 150 ℃ and 450 ℃ and the flow rate of reducing gas is 1-50mL/min/gCatalyst and process for preparing sameAnd reducing for 0.5-12h to continuously maintain carbon deposition in the molecular sieve, thereby preparing the shape selective isomerization catalyst.
2. The method of claim 1, wherein: the molecular sieve with FAU type structure is Y, Me-Y (one or more of Me ═ Zn, Mg, Mn, Co, Cr, Cu, Fe, Cd and Ni), SAPO-37, etc.
3. The method according to claim 1 or 2, characterized in that: the molecular sieve raw powder in the step (1) is a molecular sieve which is synthesized according to a conventional hydrothermal method or a solvothermal method and is not subjected to template agent removal treatment; the template agent is one or more of crown ether, tetrapropylammonium hydroxide, tetramethylammonium hydroxide and the like, and the content of the template agent is 0.5-20 wt.% of the weight of the molecular sieve.
4. The method of claim 1, wherein: the oxygen-containing atmosphere in the step (1) is oxygen or a mixed gas of oxygen and other inert atmosphere gases; the inert atmosphere is one or more than two of nitrogen, helium and argon.
5. The method of claim 1, wherein: the treatment temperature in the step (1) is 250-400 ℃, and the treatment time is 1-12 h.
6. The method of claim 1, wherein: the active component of the VIII group noble metal in the step (2) or the step (3) is one or more of Pt, Pd, Ir and other elements, and the content of the VIII group noble metal is 0.05-5.0 wt.%.
7. The method of claim 1, wherein: the reducing atmosphere in the step (3) is hydrogen or a mixed gas of hydrogen and other gases (such as one or more of nitrogen, inert gas, C1-C4 alkane, C2-C4 alkene and the like), and the flow rate of the reducing gas is 5-40mL/min/gCatalyst and process for preparing same。
8. The method of claim 1, wherein: the reduction temperature in the step (3) is 200-400 ℃, and the reduction time is 1-8 h.
9. The method of claim 1, wherein: the carbon content in the microporous pore channel of the shape selective isomerization catalyst is 0.5-16 wt% of the weight of the catalyst.
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