CN102049313A - Preparation method of load catalyst - Google Patents
Preparation method of load catalyst Download PDFInfo
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- CN102049313A CN102049313A CN2009102103285A CN200910210328A CN102049313A CN 102049313 A CN102049313 A CN 102049313A CN 2009102103285 A CN2009102103285 A CN 2009102103285A CN 200910210328 A CN200910210328 A CN 200910210328A CN 102049313 A CN102049313 A CN 102049313A
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- 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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- 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
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
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- 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
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/40—Ethylene production
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Abstract
The invention provides a preparation method of a load catalyst. The preparation method comprises the following steps of enabling a molecular sieve of a crystal silicon aluminate structure to contact with a solution containing competition adsorbent and metal ions, and then carrying out silanization treatment. The load catalyst prepared by the preparation method can improve the selectivity of C2-C4 olefins during the reaction process of converting carbinol into olefins.
Description
Technical field
The invention relates to a kind of Preparation of catalysts method, further say so about a kind of support type be used for methyl alcohol, dimethyl ether conversion is the Preparation of catalysts method of low-carbon alkene.
Background technology
Low-carbon alkene such as ethene, propylene is an important chemical material, and along with the progress and the development of modern society, its demand is increasing.Traditional ethene, propylene production all obtain in Crude Oil Processing.Because the growth of oil demand, production capacity increase the non-renewable of limited and petroleum resources, along with the rising of crude oil price, the production cost of ethene, propylene rises thereupon in recent years.For petroleum resources in short supply, there are abundant in coal resource and natural gas resource in China.Can obtain cheap synthesis gas by coal and natural gas, ripe by the technology of synthesis gas preparation methyl alcohol, therefore producing low-carbon alkene by methyl alcohol or dimethyl ether is a promising oil system alkene alternative route.
Methyl alcohol, dimethyl ether system olefin hydrocarbon need carry out under the shape selective catalysis effect of molecular sieve.ZSM-5 molecular sieve, SAPO molecular sieve are to study two kinds of catalyst activity constituent elements the most widely.For obtaining higher yield of light olefins, researchers have also carried out a series of study on the modification to molecular sieve.
U.S. Pat 7119242 and US6759360 disclose Zn have been immersed in method on the SAPO-34 molecular sieve; this method joins organic zinc in the solution of SAPO-34 molecular sieve and organic solvent under the condition of nitrogen protection; dipping finishes after steps such as centrifugal, oven dry; complicated operation, practicality are not strong.
US 5573990 provides a kind of method of the ZSM-5 molecular sieve being carried out modification.In the method, ZSM-5 mixes with Ludox and aluminum nitrate, makes cylinder shape catalyst on comminutor, and catalyst is used a certain amount of P of infusion process load or P and La again after overpickling and distilled water washing, preparation P-La-ZSM-5 catalyst after hydrothermal treatment consists.
U.S. Pat 4724275 disclosed methods are that method with ion-exchange has prepared the crystal aluminosilicate catalyst that load has VIII family metal.Specifically describe the preparation method of Pd-Y type molecular sieve catalyst among the embodiment that this patent provides, needed to finish in 20 hours ion-exchange altogether.
Be that H-ZSM-5 type molecular sieve is impregnated into the Ca (OCOCH that contains 250mL 0.1M in U.S. Pat 4579994 disclosed methods
3)
2NH with 250mL 0.1M
4H
2PO
4The aqueous solution in, and heating 1 hour under 100 ℃ water bath condition, filter then, 110 ℃ dry down, 500 ℃. roasting made the type ZSM 5 molecular sieve of Ca, P modification in 20 hours.
Used catalyst generally adopts SAPO molecular sieve and ZSM-5 molecular sieve in the methanol-to-olefins process at present, wherein SAPO molecular sieve coke selectivity is higher and cause catalysqt deactivation very fast, the selectivity of above alkene of ZSM-5 molecular sieve C4 and aromatic hydrocarbons is higher, therefore need carry out further study on the modification.
Summary of the invention
One of purpose of the present invention is the preparation method that a kind of loaded catalyst is provided on the basis of existing technology, two of purpose be with the catalyst that above-mentioned preparation method obtains be applied to methyl alcohol, dimethyl ether conversion is in the olefine reaction, to improve the selectivity of C2～C4 alkene.
Preparation method provided by the invention, it is characterized in that comprising with the molecular sieve of crystalline aluminosilicate structure with contain competitive adsorbate and contact with metal ion solution, or contact, contact with the solution of metal ion again with containing the competitive Adsorption agent solution earlier, carry out the silanization processing at last and obtain loaded catalyst.
It is the method for low-carbon alkene by methyl alcohol, dimethyl ether conversion that the present invention also provides a kind of, it is characterized in that making methyl alcohol, dimethyl ether conversion be under the condition of low-carbon alkene, and methyl alcohol, dimethyl ether are contacted with the loaded catalyst that method for preparing obtains.
The preparation method of loaded catalyst provided by the invention is simple, easy operating, realizes the industry amplification easily.The catalyst that this preparation method obtains is used for methyl alcohol, when dimethyl ether conversion is the reaction of low-carbon alkene, has excellent catalytic activity, catalytic performance good reproducibility, the selectivity height of purpose product C 2～C4 alkene.
The specific embodiment
The preparation method of loaded catalyst provided by the invention, be with the molecular sieve of crystalline aluminosilicate structure with contain competitive adsorbate and contact with metal ion solution, preferably with the method for flooding, make metal ion in molecular sieve, or concentrate the ring-type aspect under the particle surface that is distributed in, or concentrate and to be distributed in the particle center, and then carry out silanization and handle.
In the method provided by the invention, the molecular sieve of described crystalline aluminosilicate structure is conventionally known to one of skill in the art, the molecular sieve that contains crystalline aluminosilicate structure as Si-Al molecular sieve, hetero-atom molecular-sieve etc., as comprise ZSM-5, ZSM-45, ZSM-34, MCM-22, Y, BETA etc., wherein preferred ZSM-5.
In the method provided by the invention, described metal ion comes from one or more metals in IIA, the non-aluminium of IIIA family, IVA, IB, IIB, IVB, VB, VIB, VIIB, VIII and the rare earth element, one or more metals in preferred calcium, gallium, tin, copper, zinc, zirconium, vanadium, molybdenum, manganese, iron, cerium, the lanthanum.
In the method provided by the invention, described competitive adsorbate is selected from HCl, HNO
3, HF, HBr, phosphoric acid, acetic acid, tartaric acid, chloroacetic acid or citric acid, perhaps be selected from sylvite, sodium salt and the ammonium salt of above-mentioned acid one or more.Wherein, preferred competitive adsorbate is HCl, HNO
3, (NH
4)
2HPO
4, citric acid, NaBr, NH
4NO
3In one or more.
In the method provided by the invention, the mol ratio of described competitive adsorbate and metal is 0.01-10.
In the method provided by the invention, can be at first competitive adsorbate to be introduced catalyst, through the method for one or many dipping metallic element be introduced again after catalyst drying or dry and the roasting by the method for repeatedly flooding; Also can be competitive adsorbate and metallic element to be introduced catalyst simultaneously by the method for single-steeping.Wherein, be benchmark with described molecular sieve, the consumption of the solution of described metal ion makes metal component described in the molecular sieve be no more than 30 weight % in the content of oxide, preferably is no more than 10 weight %.Described metallic element is introduced in the molecular sieve with the method for dipping, and the time of dipping is preferably 0.1～6 hour.
The weight percentage of metallic element in catalyst can pass through x ray fluorescence spectrometry (XRF) and measure.The non-homogeneous load condition of metallic element in molecular sieve adopts the energy dispersive spectrometry (EDXS spectrum) on the transmission electron microscope (TEM) to measure.The percentage composition difference of metallic element on EDXS spectrum demonstration individual particle arbitrary section diverse location, then provable metallic element is non-homogeneous load condition.For example, metallic element concentration is higher and central area concentration is zero near the outer surface of individual particle arbitrary section, illustrates that then metallic element is that the eggshell type that active component concentrates on particle outer surface and the following certain thickness zone of outer surface distributes; Metallic element concentration is zero and other zone all detects certain density metallic element near the outer surface of individual particle arbitrary section, illustrates that then metallic element is the protein type that active component concentrates on surperficial following ring-type aspect; Metallic element concentration is zero and central area concentration is higher near following certain zone, the outer surface of individual particle arbitrary section and surface, illustrates that then metallic element is the yolk type that active component concentrates on the particle center.
In the method provided by the invention, described silanization processing procedure is the process of a kind of decorating molecule sieve outer surface acidity position, can use different organo-silicon compound and different Silicane Method, for example vaccum gas phase sedimentation method, mobile vapour deposition process, liquid phase deposition, backflow liquid phase deposition etc.
Vaccum gas phase sedimentation method is under certain vacuum, a certain amount of catalyst is suspended from the end of quartz fibre, catalyst after the dehydration imports adsorbate gas under different temperature, adsorbance is read by quartz electronic scale, drying and roasting generally need repeatedly repeat just can obtain satisfied load effect.Use vaccum gas phase sedimentation method, the amount of general catalyst is smaller, and it is bigger to do heavy dose of catalyst difficulty.
Mobile vapour deposition process is certain catalyst of packing in fixed bed, feeds toluene, methyl alcohol and silylating reagent at a certain temperature, behind the certain hour, and drying, roasting.
Liquid deposition comprises infusion process and circumfluence method.Infusion process adds a certain amount of molecular sieve, heating, stirring certain hour in certain density water, ethanol or the hexane solution that contains silanization reagent, after the end after filtration, dry, roasting.The backflow liquid phase deposition is to add molecular sieve, heating, stirring, backflow 1 hour in the certain density hexane solution that contains silanization reagent, finishes final vacuum and removes n-hexane, catalyst drying, roasting.
In the method provided by the invention, in the described silanization processing procedure, silylating reagent is selected from molecular formula and is (R
1)
aSi (OR
2)
b(NR
3)
cMaterial or fluosilicate, esters of silicon acis.(R
1)
aSi (OR
2)
b(NR
3)
cMiddle R
1, R
2, R
3Be identical or different alkane, alkene, cycloalkane, aromatic hydrocarbon, a, b, c are the integer between 0～4, and a+b+c=4; Preferred silylating reagent is anilinomethyl triethoxysilane, phenyl triethoxysilane, VTES, 2-(3, the 4-epoxycyclohexyl) ethyl triethoxysilane, trifluoro propyl trimethoxy silane; Preferred fluosilicate is an ammonium fluosilicate; Preferred esters of silicon acis is silicic acid four butyl esters.。When carrying out the silanization processing, the load capacity of silane is with SiO
2Meter accounts for 0.01～20% of loaded catalyst weight.
In the method provided by the invention, total silicone content of catalyst is (with SiO before and after handling
2The meter) and aluminium content (with Al
2O
3Meter) available x ray fluorescence spectrometry (XRF) is measured.The weight percentage of silane is (with SiO in the catalyst
2Meter) can calculate by following formula:
SiO
2Load capacity (%)=(R1-R2)/R2
Wherein R1 is that total silicone content of modification rear catalyst is (with SiO
2The meter) and aluminium content (with Al
2O
3Meter) ratio; R1 is that total silicone content of modification procatalyst is (with SiO
2The meter) and aluminium content (with Al
2O
3Meter) ratio.
In the method provided by the invention, preferred silanization processing method is for taking by weighing certain amount of H ZSM-5 molecular sieve and organosilan/ethanolic solution earlier 70～80 ℃ of haptoreactions, then 100～120 ℃ of dryings, in flow air in 540 ℃ of roasting 10～24h.
The inventor thinks through a large amount of research, for the active constituent catalyst with non-uniform distribution, when reaction mechanism was obeyed bimolecular Langumuir-Hinshelwood mechanism, the maximum reaction rate of reaction did not also correspond to maximum surface reaction substrate concentration, but appears at granule interior.Methanol-to-olefins is a typical bimolecular reaction process, the reaction that relates to is comparatively complicated: at first two methanol molecules are carried out the mixture that dehydration forms methyl alcohol, dimethyl ether and water very soon, oxygenate in the mixture further reaction obtains purpose product C 2～C5 light olefin, in side reactions such as the then easier generation methane decomposition in the surface of catalyst, hydrogen migrations.Therefore, active constituent is protein type or the yolk type passivation layer rear catalyst that forms shell at the catalyst outer surface that distributes simultaneously and has methanol-to-olefins process catalytic performance preferably.
The application of modification crystal aluminosilicate molecular sieve catalyst in methyl alcohol, dimethyl ether system olefin hydrocarbon of modification of surface silicon alkanisation and active constituent non-uniform Distribution do not appear in the newspapers so far yet.
The method for preparing low-carbon alkene by methyl alcohol provided by the invention comprises, is under the condition of low-carbon alkene making methanol conversion, and methyl alcohol is contacted with catalyst, and wherein, described catalyst is the above-mentioned catalyst of mentioning.In the preferred case, the described methanol conversion that makes is that the condition of low-carbon alkene comprises that the temperature of reaction is 400-550 ℃, and the pressure of reaction is normal pressure.Reactor can adopt flowing bed reactor or fixed bed reactors, and operating process can intermittently be carried out, and also can carry out continuously.
Described methanol feedstock can be to be derived from the methyl alcohol that any and several existing methods are produced.For example, by the methyl alcohol of synthesis gas preparation.According to the inventive method, can directly use as raw material by this class methyl alcohol of synthesis gas preparation.As a kind of general knowledge well known in the art, when the purification step that comprises as part or all of water in by the method separation of methanol raw material of distillation, be favourable to the efficient that improves the inventive method.In preferred embodiment, the water content in the described methyl alcohol preferably is not more than 60 weight %, further preferably is not more than 40 weight %.Described process for purification is conventionally known to one of skill in the art as distillating method.
The invention will be further described below by embodiment, but content not thereby limiting the invention.
Embodiment 1
With 100mL, concentration is the Ga (NO of 0.55mol/L
3)
3(analyze pure, Yi, a legendary monarch of Youqiong State in the xia Dynasty chemical industry Co., Ltd is won in the Guangzhou) and 10mL, concentration are that the citric acid (industrial goods, down with) of 5.5mol/L mixes, and prepare competitive adsorbate and gallium mol ratio and be 0.5 mixed solution.(the Shandong catalyst plant is produced, solid content 85.0 heavy %, Na to add 99.53g ZSM-5 molecular sieve in above-mentioned solution
2O＜0.06%), at room temperature fully stir after 2 hours and filter, drying is 3 hours under 110 ℃, again 550 ℃ of following roastings 2 hours, obtains the ZSM-5 molecular sieve Z1 of gallium element non-uniform Distribution, and the EDXS spectrum is the result show, gallium element is protein type and distributes.
0.19g 2-(3, the 4-epoxycyclohexyl) ethyl triethoxysilane is dissolved in wiring solution-forming in the 200g ethanol, again with the 70 ℃ of reactions under the condition that refluxes of Z1 and above-mentioned solution, 120 ℃ of dryings 4 hours, in 540 ℃ of roasting 24h, obtains Ga in flow air then
2O
3Content is 10 heavy %, and gallium element is the protein type distribution and silanization is handled (SiO
2Load capacity 0.05 heavy %) catalyst A is formed and preparation parameter sees Table 1.
Embodiment 2
With 100mL, concentration is the Ca (NO of 0.45mol/L
3)
2The HCl of (analyze pure, Dongxing, Shanxi chemical industry Co., Ltd) and 14.85g, 3.7 heavy % (analyzes pure, the Beijing Chemical Plant produces, down together) mixes, and prepares competitive adsorbate and calcium mol ratio and be 3.0 mixed solution.(the Shandong catalyst plant is produced, solid content 85.0 heavy %, Na to add the 57.33gZSM-5 molecular sieve in above-mentioned solution
2O＜0.06%), at room temperature fully stir after 0.5 hour and filter, drying is 3 hours under 110 ℃, again 550 ℃ of following roastings 2 hours, obtains the ZSM-5 molecular sieve Z2 of calcium constituent non-uniform Distribution, and the EDXS spectrum is the result show, calcium constituent is eggshell type and distributes.
8.33g silicic acid four butyl esters are dissolved in wiring solution-forming in the 150g n-hexane, again with the 70 ℃ of reactions under the condition that refluxes of Z2 and above-mentioned solution, 120 ℃ of dryings 4 hours, in 540 ℃ of roasting 24h, obtain CaO in flow air then
2Content is 2.67 heavy %, and calcium constituent is the eggshell type distribution and silanization is handled (SiO
2Load capacity 3.0 heavy %) catalyst B is formed and preparation parameter sees Table 1.
Embodiment 3
Be that (the Shandong catalyst plant is produced, solid content 85.0 heavy %, Na with 149.65g ZSM-5 molecular sieve for the NaBr (analyze pure, Shandong Tianxin Chemical Co., Ltd.) of 0.01mol/L with 100mL, concentration
2O＜0.06%) mix, NaBr be immersed on the ZSM-5 molecular sieve with equi-volume impregnating, place under the room temperature after 24 hours again 110 ℃ dry 3 hours down, pressed powder.With above-mentioned pressed powder and 100mL, concentration is the SnCl of 0.28mol/L
4(analyze pure, the prosperous chemical industry of Liaoyang ancient cooking vessel Co., Ltd), 100mL, concentration are the Fe (NO of 0.6mol/L
3)
3(analyze pure, transport power chemical plant, Xia County, Shanxi Province) and 50mL, concentration are that the lanthanum rich rare earth of 0.3mol/L is (with La (NO
3)
3The meter, analyze pure, the former International Trading Company Ltd of Shanghai sunlight) mix.Competitive adsorbate and metallic element mol ratio are 0.014.Above-mentioned mixed liquor at room temperature fully stirred after 4 hours filters, 110 ℃ dry 3 hours down, again 550 ℃ of following roastings 2 hours, obtain the ZSM-5 molecular sieve Z3 of metallic element non-uniform Distribution, the EDXS spectrum is the result show, metallic element all is thick eggshell type and distributes.
157.16g anilinomethyl triethoxysilane is dissolved in wiring solution-forming in the 300g ethanol, again with the 70 ℃ of reactions under the condition that refluxes of Z3 and above-mentioned solution, 120 ℃ of dryings 4 hours, in 540 ℃ of roasting 24h, obtains SnO in flow air then
2Content is 1.67 heavy %, Fe
2O
3Content is 1.92 heavy %, La
2O
3Content is 1.0 heavy %, and metallic element all is thick eggshell type distribution and silanization is handled (SiO
2Load capacity 20 heavy %) catalyst C forms and preparation parameter sees Table 1.
Embodiment 4
HNO with 5.7g 3.3 heavy %
3(analyze pure, Beijing Chemical Plant produce) is the Ce (NO of 0.08mol/L with 50mL, concentration
3)
3(analyze pure, transport power chemical plant, Xia County, Shanxi Province) and 50mL, concentration are the ammonium molybdate (molecular formula (NH of 0.023mol/L
4)
6Mo
7O
244H
2O analyzes purely, and tungsten Science and Technology Ltd. makes the country prosperous) mix, prepare competitive adsorbate and metallic element mol ratio and be 0.1 mixed solution.(the Shandong catalyst plant is produced, solid content 85.0 heavy %, Na to add 74g ZSM-5 molecular sieve in above-mentioned solution
2O＜0.06%), at room temperature fully stir after 4.5 hours and filter, drying is 3 hours under 110 ℃, again 550 ℃ of following roastings 2 hours, obtain the ZSM-5 molecular sieve Z4 of cerium and molybdenum element non-uniform Distribution, the EDXS spectrum is the result show, cerium and molybdenum element are the yolk type and distribute.
8.09g phenyl triethoxysilane is dissolved in wiring solution-forming in the 200g ethanol, again with the 70 ℃ of reactions under the condition that refluxes of Z4 and above-mentioned solution, 120 ℃ of dryings 4 hours, in 540 ℃ of roasting 24h, obtains Ce in flow air then
2O
3Content is 0.97 heavy %, MoO
2Content is 3.0 heavy %, and cerium and molybdenum element are the distribution of yolk type and silanization is handled (SiO
2Load capacity 3.0 heavy %) catalyst D forms and preparation parameter sees Table 1.
Embodiment 5
With 90mL, concentration is the NH of 1.11mol/L
4NO
3(analyze pure, Beijing Chemical Plant produce) (the Shandong catalyst plant is produced, solid content 85.0 heavy %, Na with the 106.94gZSM-5 molecular sieve
2O＜0.06%) mixes, make NH with equi-volume impregnating
4NO
3Be immersed on the ZSM-5 molecular sieve, place under the room temperature after 24 hours to descend dry 3 hours at 110 ℃ again, get pressed powder.With above-mentioned pressed powder and 100mL, concentration is the Mn (SO of 0.24mol/L
4)
2(analyze pure, the wired company of source science and technology industry of Hunan section), 100mL, concentration are the ZrOCl of 0.06mol/L
2(analyze pure, Xinghua City crane chemical reagent factory) mixes.Competitive adsorbate and metallic element mol ratio are 5.0.Above-mentioned mixed liquor at room temperature fully stirred after 4 hours filters, 110 ℃ dry 3 hours down, again 550 ℃ of following roastings 2 hours, obtain the ZSM-5 molecular sieve Z5 of metallic element non-uniform Distribution, the EDXS spectrum is the result show, metallic element all is the yolk type and distributes.
9.20g VTES is dissolved in wiring solution-forming in the 250g ethanolic solution, again with the 70 ℃ of reactions under the condition that refluxes of Z5 and above-mentioned solution, 120 ℃ of dryings 4 hours, in 540 ℃ of roasting 24h, obtains MnO in flow air then
2Content is 1.46 heavy %, ZrO
2Content is 0.51 heavy %, and manganese and zr element are the distribution of yolk type and silanization is handled (SiO
2Load capacity 3.0 heavy %) catalyst E forms and preparation parameter sees Table 1.
Embodiment 6
With 50mL, concentration is the (NH of 0.6mol/L
4)
2HPO
4(analyze pure, Tianjin Rong Hong chemical industry Co., Ltd, down with) with 50mL, concentration be the VCl of 0.6mol/L
2(analyze pure, chemical industry Co., Ltd far away in the permanent fortune in Beijing) mixes, and prepares adsorbent and metallic element mol ratio and be 1.0 mixed solution.(the Shandong catalyst plant is produced, solid content 85.0 heavy %, Na to add 69.22g ZSM-5 molecular sieve in above-mentioned solution
2O＜0.06%), at room temperature fully stir after 2 hours and filter, drying is 3 hours under 110 ℃, again 550 ℃ of following roastings 2 hours, obtains the ZSM-5 molecular sieve Z6 of v element non-uniform Distribution, and the EDXS spectrum is the result show, v element is protein type and distributes.
6.84g the trifluoro propyl trimethoxy silane is dissolved in wiring solution-forming in the 180g ethanol, again with the 70 ℃ of reactions under the condition that refluxes of Z6 and above-mentioned solution, 120 ℃ of dryings 4 hours, in 540 ℃ of roasting 24h, obtains V in flow air then
2O
5Content is 2.91 heavy %, and v element is the protein type distribution and silanization is handled (SiO
2Load capacity 3.0 heavy %) catalyst F forms and preparation parameter sees Table 1.
Embodiment 7
(NH with 0.42g citric acid and 1.06g
4)
2HPO
4Add in the deionized water of 78g, (the Shandong catalyst plant is produced, solid content 85.0 heavy %, Na to add 94.02g ZSM-5 molecular sieve after the formation clarified solution again
2O＜0.06%) mixes, make citric acid and (NH with equi-volume impregnating
4)
2HPO
4Be immersed on the ZSM-5 molecular sieve, place under the room temperature after 24 hours to descend dry 3 hours at 110 ℃ again, get pressed powder.With above-mentioned pressed powder and 50mL, concentration is the Cu (NO of 0.012mol/L
3)
2(analyze pure, the Rong Rui of Zibo City reaches powder body material factory) 50mL, concentration are the Zn (NO of 0.012mol/L
3)
4(analyze pure, transport power chemical plant, Xia County, Shanxi Province) mixes.Competitive adsorbate and metallic element mol ratio are 10.0.Above-mentioned mixed liquor at room temperature fully stirred after 4 hours filters, 110 ℃ dry 3 hours down, again 550 ℃ of following roastings 2 hours, obtain the ZSM-5 molecular sieve Z7 of metallic element non-uniform Distribution, the EDXS spectrum is the result show, metallic element all is the yolk type and distributes.
7.33g (NH
4)
2SiF
6Be dissolved in wiring solution-forming in 200 water, 70 ℃ of reactions under the condition that refluxes with Z7 and above-mentioned solution again, then 120 ℃ of dryings 4 hours, in flow air in 540 ℃ of roasting 24h, obtaining CuO content is 0.048 heavy %, ZnO content is 0.048 heavy %, and metallic element is the distribution of yolk type and silanization is handled (SiO
2Load capacity 3.0 heavy %) catalyst G forms and preparation parameter sees Table 1.
Table 1
Comparative Examples 1
This Comparative Examples illustrates molecular sieve carried metal component but does not carry out the preparation process that silanization is handled.
With 100mL, concentration is the Ca (NO of 0.45mol/L
3)
2The HCl of (analyze pure, Dongxing, Shanxi chemical industry Co., Ltd) and 14.85g, 3.7 heavy % (analyzes pure, the Beijing Chemical Plant produces, down together) mixes, and prepares competitive adsorbate and metallic element mol ratio and be 3.0 mixed solution.(the Shandong catalyst plant is produced, solid content 85.0 heavy %, Na to add 57.33g ZSM-5 molecular sieve in above-mentioned solution
2O＜0.06%), at room temperature fully stir after 0.5 hour and filter, drying is 3 hours under 110 ℃, 550 ℃ of following roastings 4 hours, obtain the ZSM-5 molecular sieve of calcium constituent non-uniform Distribution again, be designated as catalyst I, the EDXS spectrum is the result show, calcium constituent is eggshell type and distributes.
Comparative Examples 2
This Comparative Examples explanation molecular sieve does not have the carried metal component, only carries out the preparation process that silanization is handled.
8.30g silicic acid four butyl esters are dissolved in wiring solution-forming in the 150g n-hexane, (the Shandong catalyst plant is produced, solid content 85.0 heavy %, Na with 57.33g ZSM-5 molecular sieve again
2O＜0.06%) with the 70 ℃ of reactions under the condition that refluxes of above-mentioned solution,, in flow air,, obtains silanization modification (SiO in 540 ℃ of roasting 24h then 120 ℃ of dryings
2Load capacity 2.0 heavy %) ZSM-5 molecular sieve is designated as catalyst I I.
Comparative Examples 3
Catalyst is not have carried metal also not carry out the molecular sieve that silanization is handled in this Comparative Examples.
The ZSM-5 molecular sieve used with embodiment 2 is identical, and the Shandong catalyst plant is produced, solid content 85.0 heavy %, Na
2O＜0.06% 550 ℃ of following roastings 4 hours, is designated as catalyst I II before using.
Embodiment 8
The present embodiment explanation is the process of low-carbon alkene by methanol conversion.
Be reflected in the continuous fixed bed reactor synthesis under normal pressure evaluating apparatus and carry out.Behind the catalyst that filling 1.5 restrains in reactor, before reaction, purge the reactor that accommodates catalyst and temperature of reactor is risen to 550 ℃ simultaneously with nitrogen, purge and be adjusted to reaction temperature after 0.5 hour, under certain charging air speed, to feed reactor at the material benzenemethanol after the preheating section gasification, the concrete operations condition sees Table 2.The mixture that reaction produces is divided into gas-phase product and liquid product after condensation, sample analysis after 2 hours is carried out in reaction.With HP6890 type gas chromatograph on-line analysis liquid product; Form with PORAPAK-Q chromatogram column analysis gas-phase product.
Adopt following formula to calculate the selectivity and the conversion of methanol of ethene and propylene:
The moles of methanol of the moles of methanol of conversion ratio (%)=reaction consumes/input reaction
The moles of methanol of methane molal quantity/reaction consumes that methane selectively (%)=reaction generates
The moles of methanol of ethylene selectivity (%)=(ethene molal quantity * 2 that reaction generates)/reaction consumes
The moles of methanol of propylene selectivity (%)=(propylene molal quantity * 3 that reaction generates)/reaction consumes
Resulting catalyst among embodiment 1-7 and the Comparative Examples 1-3 is estimated according to the method described above, and operating condition sees Table 2.Wherein, for the catalyst B of embodiment 2 and catalyst I, II, the III of Comparative Examples 1-3 are compared, its operating condition is identical.The results are shown in Table 3.
Table 2
| The catalyst numbering | Charging air speed/g/g.h | Reaction pressure/MPa | Reaction temperature/℃ |
| A | 3.0 | Normal pressure | 480 |
| B | 3.0 | Normal pressure | 480 |
| Comparative catalyst I | 3.0 | Normal pressure | 480 |
| Comparative catalyst II | 3.0 | Normal pressure | 480 |
| Comparative catalyst III | 3.0 | Normal pressure | 480 |
| C | 5.0 | Normal pressure | 450 |
| D | 4.0 | Normal pressure | 480 |
| E | 15.0 | Normal pressure | 550 |
| F | 3.0 | Normal pressure | 480 |
| G | 3.0 | Normal pressure | 480 |
Table 3
As can be seen from Table 3, be in the reaction of low-carbon alkene by methanol conversion, adopt catalyst provided by the invention to have the selectivity of excellent catalytic activity, very high purpose product (ethene, propylene).
Claims (11)
1. the preparation method of a loaded catalyst, it is characterized in that molecular sieve that this method comprises crystalline aluminosilicate structure and contain competitive adsorbate and contact with metal ion solution, or contact, contact with the solution of metal ion again with containing the competitive Adsorption agent solution earlier, carry out silanization at last and handle.
2. according to the method for claim 1, it is characterized in that said metal is selected from one or more in IIA, the non-aluminium of IIIA family, IVA, IB, IIB, IVB, VB, VIB, VIIB, VIII and the rare earth element.
3. according to the method for claim 2, it is characterized in that said metal is selected from one or more in calcium, gallium, tin, copper, zinc, zirconium, vanadium, molybdenum, manganese, iron, cerium, the lanthanum.
4. according to the process of claim 1 wherein that said metal accounts for the 0.01-30% of molecular sieve weight in oxide.
5. according to the process of claim 1 wherein that said competitive adsorbate is selected from HCl, HNO
3, in HF, HBr, phosphoric acid, acetic acid, tartaric acid, chloroacetic acid and the citric acid one or more, perhaps be selected from sylvite, sodium salt and the ammonium salt of above-mentioned acid one or more.
6. according to the method for claim 1, it is characterized in that described containing in competitive adsorbate and the metal ion solution, the mol ratio of competitive adsorbate and metal is 0.01-10.
7. according to the method for claim 1, when said silanization was handled, the silylating reagent molecular formula was (R
1)
aSi (OR
2)
b(NR
3)
c, R
1, R
2, R
3Be identical or different alkane, alkene, cycloalkane, aromatic hydrocarbon, a, b, c are the integer between 0～4, and a+b+c=4.
8. according to the method for claim 7, said silylating reagent is selected from anilinomethyl triethoxysilane, phenyl triethoxysilane, VTES, 2-(3, the 4-epoxycyclohexyl) ethyl triethoxysilane, trifluoro propyl trimethoxy silane.
9. according to the method for claim 1, when said silanization was handled, silylating reagent was a fluosilicate.
10. according to claim 1, one of 7～9 method, when said silanization was handled, the load capacity of silylating reagent was with SiO
2Meter, its weight account for silanization and handle 0.01～20% of back loading type catalyst weight.
11. one kind is the method for low-carbon alkene by methyl alcohol, dimethyl ether conversion, it is characterized in that making methyl alcohol, dimethyl ether conversion be under the condition of low-carbon alkene, and methyl alcohol, dimethyl ether are contacted with the loaded catalyst that the method for one of claim 1-10 prepares.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104107720A (en) * | 2013-04-16 | 2014-10-22 | 中国石油化工股份有限公司 | Metal element-containing compound molecular sieve catalyst, and preparation method and application thereof |
| US9492814B2 (en) | 2013-04-08 | 2016-11-15 | Saudi Basic Industries Corporation | Catalyst for conversion of propylene to product comprising a carboxylic acid moiety |
| US10201806B2 (en) | 2013-12-20 | 2019-02-12 | Basf Se | Catalyst and process for the conversion of oxygenates to olefins |
| CN114425322A (en) * | 2020-10-15 | 2022-05-03 | 中国石油化工股份有限公司 | Supported propane dehydrogenation catalyst and preparation method thereof |
| CN114433194A (en) * | 2022-01-30 | 2022-05-06 | 烟台大学 | Preparation method and application of modified ZSM-5 gold-loaded catalyst |
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2009
- 2009-10-30 CN CN2009102103285A patent/CN102049313A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9492814B2 (en) | 2013-04-08 | 2016-11-15 | Saudi Basic Industries Corporation | Catalyst for conversion of propylene to product comprising a carboxylic acid moiety |
| CN104107720A (en) * | 2013-04-16 | 2014-10-22 | 中国石油化工股份有限公司 | Metal element-containing compound molecular sieve catalyst, and preparation method and application thereof |
| US10201806B2 (en) | 2013-12-20 | 2019-02-12 | Basf Se | Catalyst and process for the conversion of oxygenates to olefins |
| CN114425322A (en) * | 2020-10-15 | 2022-05-03 | 中国石油化工股份有限公司 | Supported propane dehydrogenation catalyst and preparation method thereof |
| CN114425322B (en) * | 2020-10-15 | 2024-03-26 | 中国石油化工股份有限公司 | Supported propane dehydrogenation catalyst and preparation method thereof |
| CN114433194A (en) * | 2022-01-30 | 2022-05-06 | 烟台大学 | Preparation method and application of modified ZSM-5 gold-loaded catalyst |
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Application publication date: 20110511 |