CN105749963A - Preparation method of hydroisomerization/cracking catalyst and catalyst - Google Patents
Preparation method of hydroisomerization/cracking catalyst and catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 39
- 238000005336 cracking Methods 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 6
- 239000002808 molecular sieve Substances 0.000 claims abstract description 71
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 71
- 239000000243 solution Substances 0.000 claims abstract description 67
- 238000000034 method Methods 0.000 claims abstract description 33
- 239000002253 acid Substances 0.000 claims abstract description 20
- 239000008367 deionised water Substances 0.000 claims abstract description 17
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000007864 aqueous solution Substances 0.000 claims abstract description 11
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000000465 moulding Methods 0.000 claims abstract description 6
- 150000003839 salts Chemical class 0.000 claims abstract description 6
- 238000001354 calcination Methods 0.000 claims abstract 6
- 239000003795 chemical substances by application Substances 0.000 claims abstract 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 32
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 22
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 22
- 239000003480 eluent Substances 0.000 claims description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims description 16
- 239000001257 hydrogen Substances 0.000 claims description 16
- 238000004898 kneading Methods 0.000 claims description 16
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 14
- 238000005470 impregnation Methods 0.000 claims description 13
- 229910017604 nitric acid Inorganic materials 0.000 claims description 11
- 229910052697 platinum Inorganic materials 0.000 claims description 11
- 239000003513 alkali Substances 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 239000012265 solid product Substances 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 claims description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 2
- -1 ammonium ions Chemical class 0.000 claims description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 2
- 150000003841 chloride salts Chemical class 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910001415 sodium ion Inorganic materials 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims 2
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 claims 1
- 238000010828 elution Methods 0.000 claims 1
- 150000002169 ethanolamines Chemical class 0.000 claims 1
- 150000002739 metals Chemical class 0.000 claims 1
- 150000002823 nitrates Chemical class 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- 239000012670 alkaline solution Substances 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 238000005406 washing Methods 0.000 abstract 2
- 230000002349 favourable effect Effects 0.000 abstract 1
- 238000001914 filtration Methods 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 238000002791 soaking Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 15
- 229910002651 NO3 Inorganic materials 0.000 description 11
- 238000006555 catalytic reaction Methods 0.000 description 10
- 238000011156 evaluation Methods 0.000 description 10
- 238000001125 extrusion Methods 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 9
- 238000006317 isomerization reaction Methods 0.000 description 7
- 239000012188 paraffin wax Substances 0.000 description 6
- 239000002283 diesel fuel Substances 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 230000008014 freezing Effects 0.000 description 4
- 238000007710 freezing Methods 0.000 description 4
- 239000010687 lubricating oil Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000002199 base oil Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000011959 amorphous silica alumina Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- CBPYOHALYYGNOE-UHFFFAOYSA-M potassium;3,5-dinitrobenzoate Chemical compound [K+].[O-]C(=O)C1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1 CBPYOHALYYGNOE-UHFFFAOYSA-M 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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Abstract
The invention relates to a preparation method of a hydroisomerization/cracking catalyst. The method specifically comprises the following steps: treating a sodium-type ZSM-22 molecular sieve containing a template agent with an alkaline solution having a certain concentration; washing the obtained product with deionized water, and performing drying and calcination to remove the template agent; performing replacement with an ammonium nitrate solution, performing filtration, washing the obtained product with deionized water, and performing drying and calcination to prepare a hydrogen-type ZSM-22 molecular sieve; mixing the hydrogen-type ZSM-22 molecular sieve with an amorphous oxide and an acid solution, and performing molding and calcination to prepare a carrier; and soaking the carrier in an aqueous solution of soluble salt, and performing drying and calcination to obtain the catalyst. Compared with a catalyst prepared in the prior art, the prepared catalyst can be used in a conversion process of wax in Fischer-Tropsch synthesis, and has favorable catalytic activity and selectivity of target products.
Description
Technical field
The invention belongs to molecular sieve catalyst field, the preparation method being specifically related to a kind of hysomer/Cracking catalyst based on ZSM-22 molecular sieve.
Background technology
F-T synthesis (Fischer-Tropschsynthesis) reacts referred to as FT, is with synthesis gas (CO and H2) synthesize the technical process of liquid fuel based on paraffin hydrocarbon when catalyst (such as ferrum system, cobalt system etc.) and appropriate reaction for raw material.Traditional F-T synthesis is characterized as being fraction distribution width, and heavy hydrocarbon content is high, and is straight-chain hydrocarbons.Such heavy paraffin hydrocarbon freezing point is high, is not as suitable as diesel oil or lubricating oil directly uses, therefore, it is necessary to its pour point depression.The main means of n-alkane pour point depression are hysomer and cracking, the bifunctional catalyst with special duct make long-chain normal paraffin be converted into the low isoparaffin of freezing point or little molecule alkane.This bifunctional catalyst is made up of acidic site and metal position two parts, and wherein acidic site is produced by the molecular sieve with special pore passage structure, such as SAPO-11, ZSM-22, ZSM-23, ZSM-5, Beta etc..
For the hydrocarbon class composition that fraction distribution is wider, if only passing through isomerization reaction, it is impossible to making all components be converted to desirable target product, such as condensation point and viscosity index (VI) can not meet demand.Therefore, occurring isomerized while, some high-melting-point normal paraffin components being not susceptible to isomerization reaction need to be carried out suitable cracking, so as to be converted into light diesel or low solidifying lubricating oil.Thus then wish that catalyst has the dual-use function of isomerization and cracking simultaneously.But excessive cracking can also make lighter products increase severely, target product (diesel oil or lubricating oil) yield step-down, both reduce the performance of product, decreased productivity, affect economic benefit.
ZSM-22 molecular sieve is the high-silica zeolite of a kind of synthetic, belongs to TON topological structure, has one-dimensional ten-ring pore passage structure, and port size isIt can adopt different template to synthesize.As US4556477 discloses a kind of method synthesizing ZSM-22 molecular sieve for template with diethylamine hydrochloride.US4902406, US5707600, US5783168 etc. disclose the method synthesizing ZSM-22 molecular sieve for template with 1,6-hexamethylene diamine.
The ZSM-22 molecular sieve silica alumina ratio of conventional method synthesis is high, and acidity is relatively strong, and acid amount is less, and micropore is the duct that molecular sieve is main.Meet the requirement with the active and suitable cracking activity of high isomerization, ZSM-22 molecular sieve must have suitable silica alumina ratio (acidity) and suitable pore-size distribution, thus carrying out while promoting isomerization and cracking and the timely desorption of reactant and product.The mode adopting post processing is molecular sieve modified to ZSM-22, it is possible to makes the silica alumina ratio of molecular sieve be adjusted, and manufactures some molecular sieve intracrystalline mesopores, thus reaching above-mentioned reaction requirement.
Summary of the invention
The preparation method that it is an object of the invention to provide a kind of hysomer-Cracking catalyst.
The present invention is achieved by the following technical solutions:
(1) by the sodium form ZSM-22 molecular sieve alkaline solution treatment containing template, with deionized water wash solid to eluent in neutrality, dry, roasting removed template method;The solid product obtained is again with ammonium nitrate (NH4NO3) solution exchange, filter, and with deionized water wash, dry, Hydrogen ZSM-22 molecular sieve is made in roasting;
(2) by gained Hydrogen ZSM-22 molecular sieve and amorphous oxide and acid solution kneading, molding, carrier is made in dry after naturally drying, roasting;
(3) by described carrier impregnation in the aqueous solution of group VIII metal soluble-salt, naturally dry be then passed through drying, roasting prepares described hysomer/Cracking catalyst.
In sodium form ZSM-22 molecular sieve in described step (1), template is one or more in diethylamine, 1,6-hexamethylene diamine, 1-butylamine or ethanolamine, and content is the 0.5-30wt.% of sodium form ZSM-22 molecular sieve.
Aqueous slkali in described step (1) is sodium hydroxide (NaOH) aqueous solution or potassium hydroxide (KOH) aqueous solution, and concentration is 0.1-1.0mol/L;Described molecular sieve base extraction is and is completely immersed in by molecular sieve in the alkali liquor that temperature is 20-120 DEG C, and the process time is 10-600min, filters after process, with deionized water wash solid to eluent in neutrality.
Being with ammonium nitrate solution exchange in described step (1) is completely immersed in ammonium nitrate solution by molecular sieve, stirring, the sodium ion on molecular sieve is made to be substituted by ammonium ion,, the sodium form ZSM-22 or the potassium type ZSM-22 molecular sieve that obtain after making base extraction are exchanged into Hydrogen ZSM-22 molecular sieve;Concentration of ammonium nitrate solution used is 0.1-1.0mol/L, and solution usage is all as the criterion with molecular sieve below liquid level;Being 20-100 DEG C by the temperature of ammonium nitrate solution exchange, exchange times is 2-4 time, each 1-8h;After each exchange is complete, filter, and with deionized water wash to eluent in neutrality.
Amorphous oxide in described step (2) is one or two or more kinds in amorphous alumina or amorphous silica-alumina, and its mass ratio with Hydrogen ZSM-22 molecular sieve is 1:10 to 10:1.
Acid solution in described step (2) is aqueous solution of nitric acid or acetic acid aqueous solution, and concentration is 0.1-1.0mol/L;Acid solution addition is molecular sieve and the 10%-100% of unformed oxide gross mass.
The concrete operation method of above-mentioned steps (2) is: mixed homogeneously with amorphous oxide by the Hydrogen ZSM-22 molecular sieve of gained in step (1), and makes support precursor by acid solution modulation, kneading;Banded extruder, tablet machine etc. is used to make support precursor molding;Dry after support precursor after molding naturally being dried, carrier is made in roasting.Wherein kneading temperature is room temperature, and the kneading time is 0.5-12h;Forming temperature is room temperature.
The aqueous solution of the group VIII metal soluble-salt in described step (3) is one or two or more kinds in the nitrate of a kind of in platinum, palladium and iridium or two kinds or three kinds, chloride salt, ammonium complex compound salt or carbonyl complex salt;Catalyst soakage adopts equi-volume impregnating, impregnates 2-12h under room temperature.
Above-mentioned in steps in baking operation before be both needed to gained solid product is dried process, baking temperature is 80-150 DEG C, and the time is 2-8h;Described sintering temperature is 300-700 DEG C, and the time is 4-40h.
Utilizing group VIII metal content in hysomer/Cracking catalyst that method provided by the invention finally prepares is 0.1-5.0wt.%.
The present invention processes means by alkali and adjusts the silica alumina ratio of molecular sieve, makes molecular sieve acid amount increase, and acid strength distribution is adjusted;Alkali processes the intracrystalline mesopore adding molecular sieve simultaneously, and when using the catalyst that this molecular sieve prepares, in course of reaction, material mass transfer is improved, and heavy linear paraffin is effectively converted, and the probability of the little further cracking of molecule isohydrocarbon reduces.
Therefore, compared with prior art, the invention have the advantages that
(1) catalyst prepared by the present invention has the isomerization performance of excellence, has good cracking performance simultaneously for heavy linear paraffin.
(2) catalyst provided by the invention can significantly improve the freezing point of diesel oil and lube base oil.
(3) catalyst prepared by the present invention is particularly well-suited to the conversion of Fischer Tropsch waxes, can be effectively improved the Determination of Diesel Oil in Fischer Tropsch waxes conversion process and lube base oil content.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is further illustrated, it is to be noted that present invention is not limited thereto.
Comparative example 1
Take 100g sodium form ZSM-22 molecular sieve after 550 DEG C of roasting 24h remove template, be placed in the NH that 2L concentration is 0.5mol/L4NO3In solution, at 60 DEG C, exchange 180min, filter, be neutrality with deionized water wash to eluent, exchange continuously (repeats above operation) twice, dries 6h at 120 DEG C, and at 550 DEG C, roasting 24h obtains Hydrogen ZSM-22 molecular sieve (H-ZSM-22).Take 30g aluminium oxide (γ-Al2O3) be mixed with uniformly, adding 80g5wt.%HNO3Solution, kneading 2h under room temperature, adopt extrusion under automatic banded extruder room temperature, naturally dry, dry 4h at 120 DEG C, at 550 DEG C, roasting 8h prepares molecular sieve carrier (H-ZSM-22 carrier).Chloroplatinic acid (H with 10mL platiniferous (Pt) 0.05g/mL2PtCl6) the above-mentioned carrier of solution impregnation 100g, prepare 0.5wt.%Pt/H-ZSM-22 catalyst, be numbered A1.Catalytic reaction evaluation result is in Table 2.
Embodiment 1
Taking 100g and contain the sodium form ZSM-22 molecular sieve of 1,6-hexamethylene diamine template, be placed in the NaOH solution that 3L concentration is 0.2mol/L, at 80 DEG C, process 180min, filter, wash to eluent in neutrality, template is removed in dry and roasting;Products therefrom is placed in the NH that 2L concentration is 0.5mol/L4NO3In solution, at 60 DEG C, exchange 180min, filter, be neutrality with deionized water wash to eluent, exchange continuously (repeats above operation) twice, dries 6h at 120 DEG C, and at 550 DEG C, roasting 24h obtains Hydrogen ZSM-22 molecular sieve (H-ZSM-22).Take 30g aluminium oxide (γ-Al2O3) be mixed with uniformly, adding 80g5wt.%HNO3Solution, kneading 2h under room temperature, adopt extrusion under automatic banded extruder room temperature, naturally dry, dry 4h at 120 DEG C, at 550 DEG C, roasting 8h prepares molecular sieve carrier (H-ZSM-22 carrier).Chloroplatinic acid (H with 10mL platiniferous (Pt) 0.05g/mL solution2PtCl6) the above-mentioned carrier of solution impregnation 100g, prepare 0.5wt.%Pt/H-ZSM-22 catalyst, be numbered B1.Catalytic reaction evaluation result is in Table 2.
Embodiment 2
Taking 100g and contain the sodium form ZSM-22 molecular sieve of 1,6-hexamethylene diamine template, be placed in the NaOH solution that 3L concentration is 0.4mol/L, at 80 DEG C, process 180min, filter, wash to eluent in neutrality, template is removed in dry and roasting;Products therefrom is placed in the NH that 2L concentration is 0.5mol/L4NO3In solution, at 60 DEG C, exchange 180min, filter, be neutrality with deionized water wash to eluent, exchange continuously (repeats above operation) twice, dries 6h at 120 DEG C, and at 550 DEG C, roasting 24h obtains Hydrogen ZSM-22 molecular sieve (H-ZSM-22).Take 30g aluminium oxide (γ-Al2O3) be mixed with uniformly, adding 80g5wt.%HNO3Solution, kneading 2h under room temperature, adopt extrusion under automatic banded extruder room temperature, naturally dry, dry 4h at 120 DEG C, at 550 DEG C, roasting 8h prepares molecular sieve carrier (H-ZSM-22 carrier).Chloroplatinic acid (H with 10mL platiniferous (Pt) 0.05g/mL solution2PtCl6) the above-mentioned carrier of solution impregnation 100g, prepare 0.5wt.%Pt/H-ZSM-22 catalyst, be numbered B2.Catalytic reaction evaluation result is in Table 2.
Embodiment 3
Taking 100g and contain the sodium form ZSM-22 molecular sieve of 1,6-hexamethylene diamine template, be placed in the NaOH solution that 3L concentration is 0.6mol/L, at 80 DEG C, process 180min, filter, wash to eluent in neutrality, template is removed in dry and roasting;Products therefrom is placed in the NH that 2L concentration is 0.5mol/L4NO3In solution, at 60 DEG C, exchange 180min, filter, be neutrality with deionized water wash to eluent, exchange continuously (repeats above operation) twice, dries 6h at 120 DEG C, and at 550 DEG C, roasting 24h obtains Hydrogen ZSM-22 molecular sieve (H-ZSM-22).Take 30g aluminium oxide (γ-Al2O3) be mixed with uniformly, adding 80g5wt.%HNO3Solution, kneading 2h under room temperature, adopt extrusion under automatic banded extruder room temperature, naturally dry, dry 4h at 120 DEG C, at 550 DEG C, roasting 8h prepares molecular sieve carrier (H-ZSM-22 carrier).Chloroplatinic acid (H with 10mL platiniferous (Pt) 0.05g/mL solution2PtCl6) the above-mentioned carrier of solution impregnation 100g, prepare 0.5wt.%Pt/H-ZSM-22 catalyst, be numbered B3.Catalytic reaction evaluation result is in Table 2.
Embodiment 4
Taking 100g and contain the sodium form ZSM-22 molecular sieve of 1,6-hexamethylene diamine template, be placed in the NaOH solution that 3L concentration is 0.8mol/L, at 80 DEG C, process 180min, filter, wash to eluent in neutrality, template is removed in dry and roasting;Products therefrom is placed in the NH that 2L concentration is 0.5mol/L4NO3In solution, at 60 DEG C, exchange 180min, filter, be neutrality with deionized water wash to eluent, exchange continuously (repeats above operation) twice, dries 6h at 120 DEG C, and at 550 DEG C, roasting 24h obtains Hydrogen ZSM-22 molecular sieve (H-ZSM-22).Take 30g aluminium oxide (γ-Al2O3) be mixed with uniformly, adding 80g5wt.%HNO3Solution, kneading 2h under room temperature, adopt extrusion under automatic banded extruder room temperature, naturally dry, dry 4h at 120 DEG C, at 550 DEG C, roasting 8h prepares molecular sieve carrier (H-ZSM-22 carrier).Chloroplatinic acid (H with 10mL platiniferous (Pt) 0.05g/mL solution2PtCl6) the above-mentioned carrier of solution impregnation 100g, prepare 0.5wt.%Pt/H-ZSM-22 catalyst, be numbered B4.Catalytic reaction evaluation result is in Table 2.
Embodiment 5
Taking 100g and contain the sodium form ZSM-22 molecular sieve of 1,6-hexamethylene diamine template, be placed in the NaOH solution that 3L concentration is 1mol/L, at 80 DEG C, process 180min, filter, wash to eluent in neutrality, template is removed in dry and roasting;Products therefrom is placed in the NH that 2L concentration is 0.5mol/L4NO3In solution, at 60 DEG C, exchange 180min, filter, be neutrality with deionized water wash to eluent, exchange continuously (repeats above operation) twice, dries 6h at 120 DEG C, and at 550 DEG C, roasting 24h obtains Hydrogen ZSM-22 molecular sieve (H-ZSM-22).Take 30g aluminium oxide (γ-Al2O3) be mixed with uniformly, adding 80g5wt.%HNO3Solution, kneading 2h under room temperature, adopt extrusion under automatic banded extruder room temperature, naturally dry, dry 4h at 120 DEG C, at 550 DEG C, roasting 8h prepares molecular sieve carrier (H-ZSM-22 carrier).Chloroplatinic acid (H with 10mL platiniferous (Pt) 0.05g/mL solution2PtCl6) the above-mentioned carrier of solution impregnation 100g, prepare 0.5wt.%Pt/H-ZSM-22 catalyst, be numbered B5.Catalytic reaction evaluation result is in Table 2.
Embodiment 6
Taking 100g and contain the sodium form ZSM-22 molecular sieve of 1,6-hexamethylene diamine template, be placed in the NaOH solution that 3L concentration is 1mol/L, at 80 DEG C, process 240min, filter, wash to eluent in neutrality, template is removed in dry and roasting;Products therefrom is placed in the NH that 2L concentration is 0.5mol/L4NO3In solution, at 60 DEG C, exchange 180min, filter, be neutrality with deionized water wash to eluent, exchange continuously (repeats above operation) twice, dries 6h at 120 DEG C, and at 550 DEG C, roasting 24h obtains Hydrogen ZSM-22 molecular sieve (H-ZSM-22).Take 30g aluminium oxide (γ-Al2O3) be mixed with uniformly, adding 80g5wt.%HNO3Solution, kneading 2h under room temperature, adopt extrusion under automatic banded extruder room temperature, naturally dry, dry 4h at 120 DEG C, at 550 DEG C, roasting 8h prepares molecular sieve carrier (H-ZSM-22 carrier).Chloroplatinic acid (H with 10mL platiniferous (Pt) 0.05g/mL solution2PtCl6) the above-mentioned carrier of solution impregnation 100g, prepare 0.5wt.%Pt/H-ZSM-22 catalyst, be numbered B6.Catalytic reaction evaluation result is in Table 2.
Embodiment 7
Taking 100g and contain the sodium form ZSM-22 molecular sieve of 1,6-hexamethylene diamine template, be placed in the NaOH solution that 3L concentration is 1mol/L, at 60 DEG C, process 240min, filter, wash to eluent in neutrality, template is removed in dry and roasting;Products therefrom is placed in the NH that 2L concentration is 0.5mol/L4NO3In solution, at 60 DEG C, exchange 180min, filter, be neutrality with deionized water wash to eluent, exchange continuously (repeats above operation) twice, dries 6h at 120 DEG C, and at 550 DEG C, roasting 24h obtains Hydrogen ZSM-22 molecular sieve (H-ZSM-22).Take 30g aluminium oxide (γ-Al2O3) be mixed with uniformly, adding 80g5wt.%HNO3Solution, kneading 2h under room temperature, adopt extrusion under automatic banded extruder room temperature, naturally dry, dry 4h at 120 DEG C, at 550 DEG C, roasting 8h prepares molecular sieve carrier (H-ZSM-22 carrier).Chloroplatinic acid (H with 10mL platiniferous (Pt) 0.05g/mL solution2PtCl6) the above-mentioned carrier of solution impregnation 100g, prepare 0.5wt.%Pt/H-ZSM-22 catalyst, be numbered B7.Catalytic reaction evaluation result is in Table 2.
Embodiment 8
Taking 100g and contain the sodium form ZSM-22 molecular sieve of 1,6-hexamethylene diamine template, be placed in the NaOH solution that 3L concentration is 1mol/L, at 60 DEG C, process 180min, filter, wash to eluent in neutrality, template is removed in dry and roasting;Products therefrom is placed in the NH that 2L concentration is 0.5mol/L4NO3In solution, at 60 DEG C, exchange 180min, filter, be neutrality with deionized water wash to eluent, exchange continuously (repeats above operation) twice, dries 6h at 120 DEG C, and at 550 DEG C, roasting 24h obtains Hydrogen ZSM-22 molecular sieve (H-ZSM-22).Take 30g aluminium oxide (γ-Al2O3) be mixed with uniformly, adding 80g5wt.%HNO3Solution, kneading 2h under room temperature, adopt extrusion under automatic banded extruder room temperature, naturally dry, dry 4h at 120 DEG C, at 550 DEG C, roasting 8h prepares molecular sieve carrier (H-ZSM-22 carrier).Chloroplatinic acid (H with 10mL platiniferous (Pt) 0.05g/mL solution2PtCl6) the above-mentioned carrier of solution impregnation 100g, prepare 0.5wt.%Pt/H-ZSM-22 catalyst, be numbered B8.Catalytic reaction evaluation result is in Table 2.
Embodiment 9
Catalytic reaction is evaluated:
Raw material: F-T synthesis heavy diesel, character is in Table 1;Reaction condition: 10mL fixed bed reactors, reaction temperature 330 DEG C, reaction pressure 8MPa, air speed 1h-1, hydrogen-oil ratio 600nL/nL.Each evaluating catalyst result is listed in table 2.
Table 1. raw oil character
Product characteristics that table 2. different catalysts is corresponding and evaluation result
Compared with comparative example, adopt catalyst prepared by the present invention can obtain higher isomerisation selectivity and target product (such as diesel oil) yield, and then make oil property be further improved (as freezing point reduces), make catalytic process economy increase simultaneously.
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