CN111215131B - Preparation method of shape selective isomerism catalyst based on MTW type structure molecular sieve - Google Patents
Preparation method of shape selective isomerism catalyst based on MTW type structure molecular sieve Download PDFInfo
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 101
- 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 101
- 239000003054 catalyst Substances 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title abstract description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 47
- 238000000034 method Methods 0.000 claims abstract description 39
- 239000012298 atmosphere Substances 0.000 claims abstract description 26
- 239000000843 powder Substances 0.000 claims abstract description 18
- 239000011148 porous material Substances 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 12
- 238000006317 isomerization reaction Methods 0.000 claims abstract description 10
- 239000002638 heterogeneous catalyst Substances 0.000 claims abstract description 9
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 8
- 238000011068 loading method Methods 0.000 claims abstract description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 27
- 230000008021 deposition Effects 0.000 claims description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 229910000510 noble metal Inorganic materials 0.000 claims description 9
- 229910052697 platinum Inorganic materials 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052754 neon Inorganic materials 0.000 claims description 3
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 3
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 3
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 3
- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical compound [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 claims description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 2
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 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
- GRVPDGGTLNKOBZ-UHFFFAOYSA-M triethyl(methyl)azanium;bromide Chemical compound [Br-].CC[N+](C)(CC)CC GRVPDGGTLNKOBZ-UHFFFAOYSA-M 0.000 claims description 2
- JAJRRCSBKZOLPA-UHFFFAOYSA-M triethyl(methyl)azanium;hydroxide Chemical compound [OH-].CC[N+](C)(CC)CC JAJRRCSBKZOLPA-UHFFFAOYSA-M 0.000 claims description 2
- 238000001027 hydrothermal synthesis Methods 0.000 claims 1
- 238000004729 solvothermal method Methods 0.000 claims 1
- 150000001335 aliphatic alkanes Chemical class 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 5
- 238000000151 deposition Methods 0.000 description 18
- 239000000047 product Substances 0.000 description 11
- 238000011156 evaluation Methods 0.000 description 8
- 238000006555 catalytic reaction Methods 0.000 description 7
- 238000012512 characterization method Methods 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 4
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 4
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003921 oil Substances 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
- 239000000376 reactant Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000003930 superacid Substances 0.000 description 2
- NJBCRXCAPCODGX-UHFFFAOYSA-N 2-methyl-n-(2-methylpropyl)propan-1-amine Chemical compound CC(C)CNCC(C)C NJBCRXCAPCODGX-UHFFFAOYSA-N 0.000 description 1
- 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
- 239000002028 Biomass Substances 0.000 description 1
- -1 SAPO-5 Chemical compound 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-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
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002199 base oil Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000000881 depressing effect Effects 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 208000020442 loss of weight Diseases 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 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
- 238000005406 washing Methods 0.000 description 1
Classifications
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- B01J35/633—
-
- 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
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/74—Noble metals
- B01J29/7469—MTW-type, e.g. ZSM-12, NU-13, TPZ-12 or Theta-3
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0207—Pretreatment of the support
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/084—Decomposition of carbon-containing compounds into carbon
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/12—Oxidising
- B01J37/14—Oxidising with gases containing free oxygen
-
- 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
- B01J2229/14—After treatment, characterised by the effect to be obtained to alter the inside of the molecular sieve channels
-
- 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
Abstract
The invention discloses a preparation method of a shape selective heterogeneous catalyst with an MTW structure molecular sieve as a carrier. The preparation method comprises the following specific steps: firstly, carrying out anaerobic roasting treatment on template-containing molecular sieve raw powder with an MTW type structure in inert atmosphere at 310-450 ℃ to carbonize the template to form carbon deposit to partially fill a molecular sieve microporous channel; then loading metal active components on the obtained molecular sieve carrier, and obtaining the target catalyst through drying and low-temperature reduction. By controlling the roasting atmosphere and temperature, the reducing temperature and the reducing gas flow rate in the molecular sieve carrier, the effective regulation and control of the depth of the molecular sieve pore channel is realized. Compared with the catalyst prepared by the prior art, the catalyst prepared by the method has higher activity and isomer yield in the normal alkane 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 heterogeneous catalyst with an MTW structure molecular sieve as a carrier.
Background
The dual-function solid catalyst is widely applied to the alkane hydroisomerization process, and consists of a hydrogenation-dehydrogenation component and an acid carrier. Wherein the hydrogenation-dehydrogenation component is mainly a group VIII metal such as Pt, pd, rh, ir and Ni, etc.; the acidic carriers can be classified into the following three categories: 1. amorphous formMono-or complex oxides, e.g. halide-treated Al 2 O 3 、SiO 2 /Al 2 O 3 Super acid ZrO 2 /SO 4 2- 、WO 3 /ZrO 2 Etc.; 2. a series of silica-alumina molecular sieves, such as Y, beta, ZSM-5, etc.; 3. aluminum phosphate molecular sieves such as SAPO-5, SAPO-11, SAPO-31, SAPO-41, etc. Molecular sieves exhibit superior performance in shape selectivity, stability, resistance to poisoning, and resistance to carbon deposition compared to amorphous oxides and superacids. Therefore, the isomerization catalyst using molecular sieve as a carrier is widely used. The patent documents of US5882505, 2004138051, 2005077209, cn1792451, 1788844, 101245260 and the like all describe in detail the preparation method of alkane hydroisomerization catalysts using molecular sieves as carriers.
In the process of molecular sieve acting on long-chain alkane hydroisomerization, the performance of the catalyst is determined by the pore canal and acidity of the catalyst. According to the theory of orifice-key shape-selective isomerization catalysis, the hydroisomerization of the linear alkane is mainly carried out on the orifice of a molecular sieve micropore, the probability of completely or mostly inserting the linear alkane into the micropore is increased, desorption is blocked, the probability of cracking at the inserting end is increased, and thus small molecular hydrocarbons are easy to generate, and the selectivity and yield of target products are reduced. The molecular sieve raw powder refers to a product obtained after the synthesis of the molecular sieve is finished, washing and drying. The removal of the organic template agent in the molecular sieve raw powder usually adopts a high-temperature roasting method, namely: the synthesized molecular sieve is directly baked at high temperature (not lower than 450 ℃) in oxygen-containing atmosphere such as air and the like to completely remove the template agent. For example, liu et al, in an air atmosphere at 550 ℃ for 8 hours to remove hexamethylenediamine as a template in ZSM-22 (J.Catal.2016, 335, 11); wang et al, in an air atmosphere at 550 ℃ for 3 hours to remove the template pyrrolidine (Ind. Eng. Chem. Res.2016,55,6069) in ZSM-23; liu et al are roasted at 600 ℃ for 6 hours in an air atmosphere to remove the template dipropylamine in the SAPO-41 (J.colloid interface.Sci.2014, 418, 193); philippaerts et al, in an air atmosphere at 550℃for 24 hours to remove the templating agent tetrapropylammonium bromide from ZSM-5 (J. Catal.2010,270, 172).
ZSM-12、NU-13. CZH-5, TPZ-12, VS-12 and Theta-3 molecular sieves are artificially synthesized aluminum silicate microporous molecular sieves, belong to MTW topological structures, have one-dimensional twelve-membered ring pore canal structures, and have pore sizes of about
It can be synthesized by using different templates. Because of the characteristics of a one-dimensional pore canal and moderate acidity, the supported catalyst taking the one-dimensional pore canal as a carrier has excellent performance in long-chain alkane hydroisomerization reaction. Similar to the molecular sieve demoulding means, the preparation of the catalyst taking the MTW molecular sieve as the carrier often adopts high-temperature (not lower than 450 ℃) roasting to remove the template agent in the molecular sieve, and the conventional high-temperature (not lower than 450 ℃) roasting demoulding means can prepare the molecular sieve carrier with completely permeable microporous channels of the molecular sieve. However, in practical use, the permeable and long microporous channels tend to inhibit the diffusion of reactants or intermediates, so that the intermediates are adsorbed to the acidic sites in the microporous channels of the molecular sieve for a long time, and secondary cracking reaction occurs, resulting in reduced selectivity and yield of target products. Therefore, the removal mode of the template agent in the molecular sieve is controlled by a new means, so that the regulation and control of the depth of microporous pore canals of molecular sieve carriers with MTW structures such as ZSM-12, NU-13, CZH-5, TPZ-12, VS-12, theta-3 and the like are realized, and the method is necessary for preparing the alkane shape-selective heterogeneous catalyst with high activity and isomer yield.
The invention provides a preparation method of a shape selective heterogeneous catalyst by taking an MTW-type structure molecular sieve as a carrier, roasting at low temperature under inert atmosphere and reducing at low temperature. Carrying out anaerobic roasting treatment on template-containing molecular sieve raw powder with an MTW type structure in inert atmosphere at low temperature to carbonize the template to form carbon deposit which partially fills the microporous channels of the molecular sieve; then loading metal active components on the obtained molecular sieve carrier, and obtaining the target catalyst through drying and low-temperature reduction. The in-situ generation of carbon deposition in the molecular sieve pore canal is realized by controlling the roasting atmosphere and temperature, the reducing temperature and the reducing gas flow rate in the molecular sieve carrier, so that the depth of the molecular sieve pore canal is effectively regulated and controlled. Compared with the catalyst prepared by the prior art, the catalyst prepared by the method has higher activity and multi-branched isomer yield in the normal alkane isomerization reaction.
Disclosure of Invention
The invention aims to provide a preparation method of a shape selective isomerism catalyst based on an MTW type structure molecular sieve.
The invention also relates to the application of the catalyst in the isomerization reaction of alkane.
Specifically, the preparation method of the catalyst provided by the invention is characterized in that: the MTW type structure molecular sieve carrier is subjected to oxygen-free low-temperature roasting in an inert atmosphere at a lower temperature (not higher than 450 ℃), then is loaded with metal, is dried, and is reduced by controlling the flow rate of a reducing atmosphere at a low temperature, so that the shape selective heterogeneous catalyst is prepared, and comprises the following steps:
(1) Roasting the molecular sieve raw powder containing the template agent and having an MTW type structure for 0.5-24 hours at the temperature of 310-450 ℃ in one or more than two of inert atmosphere such as nitrogen, helium, neon and argon, and converting the template agent contained in the molecular sieve raw powder into carbon deposit to be filled in a molecular sieve pore channel;
(2) Loading the calcined molecular sieve in the step (1) with active components of noble metal of the VIII family, drying, and controlling the flow rate of the reducing gas to be 5-50mL/min/g in a reducing atmosphere at 100-400 DEG C Catalyst Reducing for 1-12h to keep carbon deposition in micropores of the molecular sieve, thus obtaining the shape selective heterogeneous catalyst.
The molecular sieve with MTW type structure in the method provided by the invention is one or more of ZSM-12, NU-13, CZH-5, TPZ-12, VS-12 and Theta-3;
the template agent in the step (1) of the method provided by the invention is organic amine filled in the pore canal of the MTW-type structural molecular sieve, and is derived from the synthesis process of the MTW-type structural molecular sieve, and the template agent comprises organic amine such as tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetraethylammonium bromide, tetrapropylammonium bromide, methyltriethylammonium hydroxide, methyltriethylammonium bromide and the like or a mixture of the organic amine and the organic amine;
the noble metal active component loading process in the method step (2) provided by the invention adopts the conventional operation in the field, including but not limited to dipping, precipitation, deposition, adhesive bonding or mechanical pressing and other operations, so that the group VIII noble metal precursor is dispersed on the carrier, and the combination of the group VIII noble metal and the carrier is realized; the metal precursors used include, but are not limited to, metal acids, metal acid salts, chlorides, ammonia complexes, carbonyl complexes, or mixtures thereof;
the inert atmosphere in the step (1) of the method provided by the invention is one or more of nitrogen, helium, neon and argon;
the roasting temperature in the step (1) of the method provided by the invention is 310-450 ℃, which is lower than the temperature required by complete removal of the template agent in the molecular sieve, and the treatment temperature is 310-400 ℃ preferably;
the roasting time in the step (1) of the method provided by the invention is 0.5-24h, preferably 1-12h;
the roasting process in the step (1) of the method provided by the invention enables the template agent in the MTW type molecular sieve raw powder to be converted into carbon deposit and fills part of molecular sieve microporous channels, wherein the proportion of the total weight of the carbon deposit in the roasted MTW type molecular sieve microporous channels to the weight of the molecular sieve is 0.2-10wt.%;
the roasting process in the step (1) of the method provided by the invention enables the template agent in the MTW type molecular sieve raw powder to be converted into carbon deposit and fills part of molecular sieve microporous channels, and the preferred proportion of the total weight of the carbon deposit in the roasted MTW type molecular sieve microporous channels to the weight of the molecular sieve is 0.5-5wt.%;
the active component of the VIII family noble metal in the method step (2) provided by the invention is one or more of Pt, pd, ir, ru, rh and other elements, and the content of the VIII family noble metal is 0.05-5.0 wt%, preferably 0.1-3.0 wt%;
the drying temperature in the step (2) of the method provided by the invention is 20-200 ℃, and the drying time is 0.5-24h; preferably the drying temperature is 70-150 ℃, preferably the drying time is 2-8h;
the reduction mode in the step (2) of the method provided by the invention adopts one or two of reducing atmosphere such as hydrogen and carbon monoxide to contact with the catalyst to reduce the catalyst;
the gas flow rate of the reducing atmosphere in the step (2) of the method provided by the invention is 5-50mL/min/g of catalyst; preferably, the gas flow rate is 5-30mL/min/g of catalyst;
the reduction temperature in the step (2) of the method provided by the invention is 100-450 ℃, and the reduction time is 1-12h; preferably the reduction temperature is 200-400 ℃, preferably the reduction time is 2-8h;
the reduction process in the step (2) of the method provided by the invention keeps the carbon deposit generated in the step (1) in the microporous channels of the molecular sieve;
the micropore carbon content in the shape selective isomerism catalyst in the step (2) of the method provided by the invention is 0.5-5wt% of the weight of the catalyst.
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 isomerization pour point depressing, isomerization dewaxing and the like.
Compared with the traditional preparation method of the hydroisomerization catalyst with the permeable microporous channels obtained by roasting and de-molding at high temperature (not lower than 450 ℃), the preparation method of the catalyst provided by the invention has the following advantages:
1. the roasting 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 deposit generated in situ in the preparation process partially fills the microporous channels of the molecular sieve, shortens the depth of the channels, shortens the carbon chain length of the adsorbate inserted into the microporous channels, and obviously improves the mass transfer of reactants and intermediate products;
3. the prepared shape selective isomerization catalyst has higher activity and isomer yield in alkane isomerization reaction, in particular to multi-branched isomer yield; the method is applied to the processing process of petroleum fractions, biomass and Fischer-Tropsch synthesis products, and can obviously improve the product yield and improve the product performance, such as the octane number of gasoline products, the cetane number of diesel products, the pour point of lubricating oil base oil products and the like.
Detailed Description
The present invention will be further described with reference to specific examples, but it should be noted that the present invention is not limited thereto.
And determining the carbon deposition and organic matter content of the sample according to the thermogravimetric analysis result. The samples were thermogravimetric measured using a model STA 449 F3 instrument from NETZSCH, germany. Measurement conditions: the sample loading was 20mg and the temperature was raised from 40℃to 900℃in an air atmosphere (flow 20 ml/min) at a temperature-raising rate of 10℃per minute. The carbon content of the sample is the loss of weight of the sample at a temperature of more than 400 ℃ in the result of thermal weight of the sample.
The pore volume measurement of the samples was performed on a Micromeritics ASAP2420 physical adsorption instrument. Before testing, the sample was evacuated at 200℃for 6h and then N was applied at liquid nitrogen temperature 2 Determination of adsorption and desorption isotherms. The micropore volume of the sample was calculated by the t-plot method.
Catalyst evaluation was performed in a stainless steel tube fixed bed reactor, 10mL of the prepared catalyst was placed in the reactor, the temperature was raised to the reaction temperature under a hydrogen atmosphere, the reaction was performed by passing n-hexadecane as a raw oil, and the product was analyzed by gas chromatography. Reaction conditions: the reaction temperature is 290-360 ℃, the pressure is 10MPa, and the liquid hourly space velocity of the n-hexadecane is 1.0h -1 The hydrogen to oil ratio (mol/mol) was 15.
Comparative example
120g of ZSM-12 molecular sieve raw powder containing tetraethylammonium hydroxide template agent (the content is 10wt.% of the weight of the molecular sieve) is taken and baked for 18 hours in an air atmosphere at 550 ℃ to obtain about 100g of ZSM-12 molecular sieve carrier with the template agent completely removed, wherein the carbon content in the molecular sieve carrier is 0, and the micropore volume is 0.050cm 3 And/g. With 5mL of H containing Pt 0.05g/mL 2 PtCl 6 50g of the above carrier was impregnated with the solution, naturally dried and dried at 120℃for 4 hours, and reduced with hydrogen at 500℃for 4 hours to prepare 0.5wt.% Pt/ZSM-12 catalyst. The carbon content in the catalyst is 0, and the micropore volume is 0.050cm 3 And/g. The characterization results of the carbon deposition content and the micropore volume of the catalyst are shown in table 1, and the evaluation results of the catalytic reaction are shown in table 2.
Example 1
120g of ZSM-12 molecular sieve raw powder containing tetrabutylammonium hydroxide template agent (the content is 10wt.% of the weight of the molecular sieve) is taken, and 3 g of ZSM-12 molecular sieve raw powder is takenRoasting for 12 hours at 20 ℃ under nitrogen atmosphere to obtain about 105g of ZSM-12 molecular sieve carrier with microporous channels partially filled with carbon deposit, wherein the carbon deposit content of the molecular sieve carrier is 5.0wt.%, and the micropore volume is 0.019cm 3 And/g. With 5mL of H containing Pt 0.05g/mL 2 PtCl 6 The solution is immersed in 50g of the carrier, naturally dried and dried for 4h at 120 ℃, the hydrogen flow rate is controlled to be 5mL/min/g of catalyst at 400 ℃, and the catalyst is reduced for 8h, thus obtaining 0.5wt.% Pt/ZSM-12 catalyst. The carbon content in the catalyst was 5.0wt.%, and the micropore volume was 0.019cm 3 And/g. The characterization results of carbon deposition and micropore volume of the catalyst are shown in table 1, and the evaluation results of the catalytic reaction are shown in table 2.
Example 2
120g of TPZ-12 molecular sieve raw powder containing tetrabutylammonium hydroxide template agent (the content is 12wt.% of the weight of the molecular sieve) is taken and baked for 8 hours under the nitrogen atmosphere of 350 ℃ to obtain about 105g of TPZ-12 molecular sieve carrier with partially filled micropore channels by carbon deposition, wherein the carbon deposition content of the molecular sieve carrier is 4.8wt.% and the micropore volume is 0.020cm 3 And/g. With 5mL of H containing Pt 0.05g/mL 2 PtCl 6 The solution is immersed in 50g of the carrier, naturally dried and dried for 4h at 120 ℃, the hydrogen flow rate is controlled to be 10mL/min/g of catalyst at 350 ℃, and the catalyst is reduced for 6h, thus preparing 0.5wt.% Pt/TPZ-12 catalyst. The carbon content in the catalyst is 0, and the micropore volume is 0.020cm 3 And/g. The characterization results of carbon deposition and micropore volume of the catalyst are shown in table 1, and the evaluation results of the catalytic reaction are shown in table 2.
Example 3
120g of NU-13 molecular sieve raw powder containing di-n-butylamine template agent (the content is 20wt.% of the weight of the molecular sieve) is taken and baked for 6 hours in argon atmosphere at 360 ℃ to obtain about 105g of NU-13 molecular sieve carrier with microporous channels partially filled with carbon deposit, wherein the carbon deposit content of the molecular sieve carrier is 4.0wt.% and the micropore volume is 0.023cm 3 And/g. With 5mL of H containing Pt 0.05g/mL 2 PtCl 6 The solution is immersed in 50g of the carrier, naturally dried and dried for 4h at 120 ℃, the hydrogen flow rate is controlled to be 20mL/min/g of catalyst at 300 ℃, and the catalyst is reduced for 4h, thus preparing 0.5wt.% Pt/NU-13 catalyst. The carbon content in the catalyst was 4.0wt.%, and the micropore volume was 0.023cm 3 And/g. The characterization result of the carbon deposition content and micropore volume of the catalyst is shown in the table1, and the evaluation results of the catalytic reaction are shown in Table 2.
Example 4
120g of VS-12 molecular sieve raw powder containing di-n-butylamine template agent (the content is 6wt.% of the molecular sieve weight) is taken and baked for 4 hours at 380 ℃ under nitrogen atmosphere to obtain about 101g of VS-12 molecular sieve carrier with partially filled micropore channels by carbon deposition, wherein the carbon deposition content of the molecular sieve carrier is 2.0wt.% and the micropore volume is 0.035cm 3 And/g. With 5mL of H containing Pt 0.05g/mL 2 PtCl 6 The solution is immersed in 50g of the carrier, naturally dried and dried for 4h at 120 ℃, the hydrogen flow rate is controlled to be 25mL/min/g of catalyst at 250 ℃, and the catalyst is reduced for 4h, thus preparing 0.5wt.% Pt/VS-12 catalyst. The carbon content in the catalyst was 2.0wt.%, and the micropore volume was 0.035cm 3 And/g. The characterization results of the carbon deposition content and the micropore volume of the catalyst are shown in table 1, and the evaluation results of the catalytic reaction are shown in table 2.
Example 5
120g of Theta-3 molecular sieve raw powder containing diisobutylamine and diethylamine template agent (the content is 10wt.% of the weight of the molecular sieve) is taken and baked for 3 hours in nitrogen atmosphere at 400 ℃ to obtain about 105g of Theta-3 molecular sieve carrier with partially filled micropore channels by carbon deposition, wherein the carbon deposition content of the molecular sieve carrier is 0.5wt.%, and the micropore volume is 0.039cm 3 And/g. With 5mL of H containing Pt 0.05g/mL 2 PtCl 6 The solution was impregnated with 50g of the above-mentioned carrier, naturally dried and dried at 120℃for 4 hours, and the hydrogen flow rate was controlled at 30mL/min/g catalyst at 200℃and reduced for 2 hours to prepare 0.5wt.% Pt/Theta-3 catalyst. The carbon content in the catalyst was 0.5wt.%, and the micropore volume was 0.039cm 3 And/g. The characterization results of the carbon deposition content and the micropore volume of the catalyst are shown in table 1, and the evaluation results of the catalytic reaction are shown in table 2.
TABLE 1 characterization of the catalysts in the comparative examples and examples
TABLE 2 evaluation results of catalysts in comparative examples and examples
As can be seen from Table 1, the template agent was thoroughly removed by a conventional method in the comparative example, and the MTW-structured molecular sieve carrier (ZSM-12) had a carbon deposition content of 0, and the microporous channels were completely permeable. In examples 1-5, the MTW structure molecular sieve carrier (ZSM-12, TPZ-12, NU-13, VS-12, theta-3) obtained by the method for converting the template agent into carbon deposit has carbon deposit, the molecular sieve pore volume is reduced, part of micropore pore channels are filled, and the depth of the micropore pore channels is shortened.
As can be seen from Table 2, the catalysts prepared in examples 1 to 5 obtained higher activity and isomer yields, particularly the multi-branched isomer yields, in the alkane hydroisomerization reactions than the catalysts prepared in the conventional methods in the comparative examples.
Claims (8)
1. A method for preparing a shape selective heterogeneous catalyst by taking an MTW type structure molecular sieve as a carrier is characterized in that the MTW type structure molecular sieve carrier is subjected to low-temperature anaerobic roasting in inert atmosphere to convert a template agent contained in a molecular sieve pore path into carbon deposit, the carbon deposit is partially filled in a molecular sieve micropore duct, then metal is loaded, and the carbon deposit in the molecular sieve micropore is continuously maintained through drying and low-temperature reduction, so that the shape selective heterogeneous catalyst is prepared, and the method comprises the following steps:
(1) Roasting the molecular sieve raw powder containing the template agent and having an MTW structure at the temperature of between 310 and 450 ℃ in an inert atmosphere for 0.5 to 24 and h, and converting the template agent contained in the molecular sieve raw powder into carbon deposit to be filled in a molecular sieve pore channel;
(2) Loading the calcined molecular sieve in the step (1) with a group VIII noble metal active component, drying, and controlling the flow rate of a reducing gas to be 5-50mL/min/g of catalyst in a reducing atmosphere at 100-400 ℃ to reduce 1-12h so as to continuously maintain carbon deposition in micropores of the molecular sieve, thereby preparing the shape selective heterogeneous catalyst;
the molecular sieve with MTW type structure is one or more than two of ZSM-12, NU-13, CZH-5, TPZ-12, VS-12 and Theta-3.
2. The method according to claim 1, characterized in that: the molecular sieve raw powder in the step (1) is synthesized according to a conventional hydrothermal method or a solvothermal method, and is not subjected to template agent removal treatment; the template agent in the step (1) is one or more than two of tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetraethylammonium bromide, tetrapropylammonium bromide, methyltriethylammonium hydroxide and methyltriethylammonium bromide, and the content of the template agent is 0.5-20 wt% of the weight of the molecular sieve.
3. The method according to claim 1, characterized in that: the inert atmosphere in the step (1) is one or more than two of nitrogen, helium, neon and argon, the roasting temperature is 310-400 ℃, and the roasting time is 1-12 h.
4. A method as claimed in claim 1, characterized in that: the active component of the VIII family noble metal in the step (2) is one or more than two of Pt, pd, ir, ru, rh elements, and the content of the VIII family noble metal is 0.05-5.0wt percent.
5. A method as claimed in claim 1, characterized in that: the drying temperature in the step (2) is 50-200 ℃; the drying time is 0.5-24 and h.
6. A method as claimed in claim 1, characterized in that: the reducing atmosphere in the step (2) is one or two of hydrogen and carbon monoxide; the gas flow rate of the reducing atmosphere is 5-30mL/min/g of catalyst.
7. A method as claimed in claim 1, characterized in that: the reduction temperature in the step (2) is 200-400 ℃ and the reduction time is 2-8 h.
8. A method as claimed in claim 1, characterized in that: the carbon content in micropores of the shape selective isomerization catalyst is 0.5-5wt% of the weight of the catalyst.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108126735A (en) * | 2016-12-01 | 2018-06-08 | 中国科学院大连化学物理研究所 | A kind of isomerization catalyst and preparation and application |
| CN108126737A (en) * | 2016-12-01 | 2018-06-08 | 中国科学院大连化学物理研究所 | A kind of alkane hydroisomerization catalyst and preparation and application |
| CN108144645A (en) * | 2016-12-04 | 2018-06-12 | 中国科学院大连化学物理研究所 | A kind of alkane isomerization catalyst and its preparation and application |
| CN108144644A (en) * | 2016-12-04 | 2018-06-12 | 中国科学院大连化学物理研究所 | A kind of hydroisomerisation catalysts and its preparation and application |
| CN108144653A (en) * | 2016-12-04 | 2018-06-12 | 中国科学院大连化学物理研究所 | A kind of oil hydrogenation catalyst preparation and catalyst and application |
| CN108144651A (en) * | 2016-12-04 | 2018-06-12 | 中国科学院大连化学物理研究所 | A kind of catalyst for hydroisomerizing and its preparation and application |
-
2018
- 2018-11-26 CN CN201811415533.0A patent/CN111215131B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108126735A (en) * | 2016-12-01 | 2018-06-08 | 中国科学院大连化学物理研究所 | A kind of isomerization catalyst and preparation and application |
| CN108126737A (en) * | 2016-12-01 | 2018-06-08 | 中国科学院大连化学物理研究所 | A kind of alkane hydroisomerization catalyst and preparation and application |
| CN108144645A (en) * | 2016-12-04 | 2018-06-12 | 中国科学院大连化学物理研究所 | A kind of alkane isomerization catalyst and its preparation and application |
| CN108144644A (en) * | 2016-12-04 | 2018-06-12 | 中国科学院大连化学物理研究所 | A kind of hydroisomerisation catalysts and its preparation and application |
| CN108144653A (en) * | 2016-12-04 | 2018-06-12 | 中国科学院大连化学物理研究所 | A kind of oil hydrogenation catalyst preparation and catalyst and application |
| CN108144651A (en) * | 2016-12-04 | 2018-06-12 | 中国科学院大连化学物理研究所 | A kind of catalyst for hydroisomerizing and its preparation and application |
Non-Patent Citations (1)
| Title |
|---|
| 模板剂脱除方式对Pt/ZSM-23烷烃异构化性能的影响;吕广等;《石油学报(石油加工)》;20180725(第04期);第696-704页 * |
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