CN103130604A - Method of using modified molecular sieve catalyst in isobutane catalytic cracking - Google Patents

Method of using modified molecular sieve catalyst in isobutane catalytic cracking Download PDF

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CN103130604A
CN103130604A CN2013100505995A CN201310050599A CN103130604A CN 103130604 A CN103130604 A CN 103130604A CN 2013100505995 A CN2013100505995 A CN 2013100505995A CN 201310050599 A CN201310050599 A CN 201310050599A CN 103130604 A CN103130604 A CN 103130604A
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reaction
carrier
catalyst
molecular sieve
trimethylmethane
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郭洪臣
刘家旭
艾沙努拉洪
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Dalian University of Technology
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Dalian University of Technology
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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
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    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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Abstract

The invention discloses a method of using modified molecular sieve catalyst in isobutane catalytic cracking and belongs to the technical field of catalysts. The method includes the following steps: conducting full negative pressure degassing purification treatment on a molecular sieve, adopting a negative pressure deposition-precipitation method to load a gold precursor to a molecular sieve carrier, and obtaining an even and high-dispersion small particular supported gold catalyst. The molecular sieve is a high-silica zeolite molecular sieve, the supported gold catalyst obtained by the deposition-precipitation method under the condition of negative pressure is beneficial for purifying the inner surface, the outer surface and a duct of the molecular sieve, and Au can easily enter the duct of the molecular sieve to achieve high dissipation. By means of the method, dehydrogenation is conducted on isobutane to produce olefin under double functions of metal and a carrier, the olefin obtains a proton at an acid center to form a carbonium ion, and the carbonium ion conducts polymer lysis to generate a corresponding olefin.

Description

A kind of modified molecular sieve catalyst is for the method for Trimethylmethane catalytic pyrolysis
Technical field
The invention belongs to catalyst technical field, relate to the application of a kind of modified molecular sieve catalyst in the Trimethylmethane catalytic cracking reaction.
Background technology
Ethene, propylene and iso-butylene that the devices such as the catalytic cracking of Petrochemical Enterprises and steam cracking are produced are very important polymer monomers.Simultaneously, iso-butylene is also for the synthesis of MTBE.So have limitation but merely from expansion refining of petroleum amount, increase production these useful alkene because petroleum resources are day by day exhausted.On the other hand, some iso-butylene relative surplus local as that China is produced by catalytic cracking unit urgently develops in the world.Trimethylmethane is changed into to these important industrial chemicals of ethene, propylene and iso-butylene efficiently by scission reaction very useful to improving the crude oil utilization ratio.Trimethylmethane is existing utilizes method as follows:
One, preparing isobutene through dehydrogenation of iso-butane:
Patent CN1071410A(1993) disclosed a kind of method that lower paraffin hydrocarbons prepares alkene.It is characterized in that: the metallic elements such as Fe, Cr, Ni, Pt, Pd of take are active ingredient, Al 2o 3or adopt preparation catalyst for carrier on aluminosilicate zeolite.
Patent CN101618319A (2010) has disclosed a kind of CrOx/ mesoporous CaO Catalysts and its preparation method of efficient producing isobutene from oxidative dehydrogenation of isobutane.It is characterized in that: take CrOx as active ingredient, take mesoporous CaO as carrier, adopt preparation catalyst.
Patent CN102059111A (2011) has disclosed a kind of catalyzer for generating high-value olefins from liquefied petroleum gas and preparation and application.It is characterized in that: take chromic salts, rare earth, basic metal etc. is active ingredient, in kaolin and pseudo-boehmite slurries, adds solution then to regulate the method Kaolinite Preparation of Catalyst that pH value generates gel.
Patent CN101862669A (2010) has disclosed a kind of catalyst for preparing isobutene through dehydrogenation of iso-butane and preparation method thereof.It is characterized in that: used additives basic metal is the support modification agent, adopts H 2ptCl 6and Sncl 4mixed aqueous solution be immersed on the stanniferous mesoporous aluminum oxide molecular sieve carrier of skeleton and make catalyzer.
Patent CN102000593A(2010) disclose a kind of dehydrogenation of isobutane and produced the preparation method of iso-butylene with catalyzer.It is characterized in that: using Pt as Primary Catalysts, Sn, potassium and chlorine are as promotor, with Al 2o 3for carrier, adopt pickling process to make the dehydrogenation of isobutane catalyzer.
Patent CN102070391A (2011) has disclosed a kind of method that fully utilizes the mixed c 4 preparing isobutene.It is characterized in that: take metallic nickel, zinc or palladium as active ingredient, take aluminum oxide as carrier, adopt preparation catalyst.
Patent CN1044787C (1999) has disclosed a kind of producing isobutene from oxidative dehydrogenation of isobutane catalyzer and manufacture method thereof.It is characterized in that: the oxide compound of Mg, Ca, Sr or Ba and muriate are mixed and made into to catalyzer by certain mol proportion.
Patent CN1073464A (1996) has disclosed a kind of catalyst for dehydrogenation of low-carbon paraffin and method for making thereof.It is characterized in that: take Pt, Sn as active ingredient, using MgAl(O) composite oxides are as carrier, adopt the co-impregnation Kaolinite Preparation of Catalyst.
Patent CN1086150C (2002) has disclosed a kind of catalyzer and application thereof of producing isobutylene by catalytic dehydrogenation of isobutane.It is characterized in that: take Cr, K, Cu or La as active ingredient, Al 2o 3for the carrier Kaolinite Preparation of Catalyst, adopt preparation catalyst.
Patent CN101138738B (2011) has disclosed the preparation method of a kind of CrOx/SBA-15 as isobutene for oxo-dehydrogenation producing of isobutylene catalyzer.It is characterized in that: take Cr as active ingredient, the SBA-15 molecular sieve is carrier, adopts preparation catalyst.
Patent CN101439292A (2009) has disclosed a kind of producing isobutene from oxidative dehydrogenation of isobutane solid catalyst and method for making thereof.It is characterized in that: the main body of catalyzer is phosphato-molybdic heteropolyacid an alkali metal salt-nickel oxide matrix material or phosphato-molybdic heteropolyacid alkaline earth salt-nickel oxide matrix material, adopts the Cs ion as additive.
Patent US4469811 (1984) has disclosed a kind of preparation method of C2-C4 alkane dehydrogenating catalyst.It is characterized in that: take Pt and Sn as active ingredient, with Al 2o 3for carrier, the Soaking Kaolinite Preparation of Catalyst.
Patent US4849567 (1989) has disclosed a kind of preparation method of C2-C5 saturated alkane dehydrogenation catalyst.It is characterized in that: take Pt and In as active ingredient, take ZSM-5 as carrier, the Soaking Kaolinite Preparation of Catalyst.
Patent US4886926 (1989) has disclosed a kind of preparation method of the non-acidic zeolite molecular sieve C2-C5 saturated alkane dehydrogenation catalyst containing Sn.It is characterized in that: take Sn and Pt as active ingredient, take ZSM-5 as carrier, the Soaking Kaolinite Preparation of Catalyst.
Patent US4962266 (1990) has disclosed a kind of preparation method of normal butane dehydrogenation catalyst.It is characterized in that: take Pt as active ingredient, with Al 2o 3or containing zinc SiO 2oxide compound is carrier, the Soaking Kaolinite Preparation of Catalyst.
Patent US5019664 (1991) has disclosed a kind of preparation method of C2-C12 alkane dehydrogenating catalyst.It is characterized in that: take Ca, Sr as active ingredient, take the MCM-22 molecular sieve as carrier, the Soaking Kaolinite Preparation of Catalyst.
Patent US5122489 (1992) has disclosed a kind of preparation method of alkane dehydrogenating catalyst.It is characterized in that: take Ru, Re, Ir is active ingredient, and take Pt, Pd load micro-pore zeolite material is carrier, the Soaking Kaolinite Preparation of Catalyst.
Patent US5146034 (1991) has disclosed a kind of preparation method of alkane dehydrogenating catalyst.It is characterized in that: take Zn as active ingredient, take ZSM-5 molecular sieve as carrier, the Soaking Kaolinite Preparation of Catalyst.
Patent US5146034 (1991) has disclosed a kind of preparation method of alkane dehydrogenating catalyst.It is characterized in that: take Zn as active ingredient, take ZSM-5 molecular sieve as carrier, the Soaking Kaolinite Preparation of Catalyst.
Also have a lot of patents to relate to the dehydrogenation of isobutane catalyzer, as:
Relate to platinum, the catalyzer patent that palladium is active ingredient: US7943038B2(2008), US7012038B2(2002), US6197717B1(2000), US6197717B1(2000), US6498280B1(2000), US6103103A (1999), US6576804B1(1999), EP0894781A1(1998), WO9929420A1(1998), WO9601238A1(1995), CN1046122C(1995), EP0768994A1(1995), EP0768995A1(1995), EP0768995B1(1995), CN1151723A(1995), WO9601238A1(1995), US5453558A (1994), SG52554A1(1994), KR100211630B1(1994), US5430220A(1994), EP0614698A1(1994), CA2117104A1(1994), US5476982A(1994), US3864284A(1993), US19930055343(1993), US5258567A(1992), JP2311425A(1990), AU622274B2(1990), US4880764A(1988)) JP62126140A(1986), EP0228792A1(1986), US4677237A(1986), EP0212850A1(1986), US4665267A(1986), US4766266A(1985), US4409417A(1982), US4216346A(1979), US4104317A(1977), US4128590A(1977), US4104317A(1977).
The catalyzer patent that to relate to gallium be active ingredient: EA012015B1(2005), US2004199034A1(2004), EP1492620A1(2003), US2003202934A1(2003), EP1442000A1(2002), WO03033440A1(2002), EP1442000A1(2002), EP0614698A1(1994), CA2117104A1(1994), US5476982A(1994), EP0614698A1(1994) US5476982A(1994), US5346871A(1993).
The catalyzer patent that to relate to nickel be active ingredient: US7498289B2(2007), US7674944B2(2007), US7626068B2(2007), US2007197378A1 (2007), US2007191665A1(2007), US2007197847A1(2007), , US7626068B2(2007), WO2007118806A1(2007) US7227049B2(2003), US2005090702A1(2003), US2005187420A9(2003), , US2005090702A1(2003), US7227049B2(2003), US2003097034A1(2001), US2002055664A1(2001), US6777371B2(2001), US6417422B1(2000), US6436871B1(1999), US5563314A(1995), US5043461A(1990), US3670044A(1969), GB1250786A(1968).
The catalyzer patent that to relate to molybdenum, cobalt be active ingredient: WO2009028700A1(2008), US6635794B2(2001), US6586649B1(2001), WO0112321A1(2000), US5086032A(1991), FR2642669A1(1989), US4255284A(1978), US4131631A(1975), US4035261A(1975), US3840472A(1970), US3755150A(1968).
The catalyzer patent that to relate to chromium be active ingredient: US2010312035A1(2009), WO2010009076A3(2009), CN102123790A(2009), EP2300157A2(2009), WO2007030298A1(2006), US7622623B2(2005), US2006094914A1(2005), US7176335B2(2003), EP1534655A1(2003), RU2005100036A(2003), RU2323043C2(2003), EP1534655A1(2003), RU2323043C2(2003), US6797850B2(2002), US2003232720A1(2002), US7012038B2(2002), US2003232720A1(2002), US6475950B2(2001), US6475950B2(2001), US2001046942A1(2001), SG82039A1(1989), EP0212850A1(1986), US4665267A(1986), US4067924A(1976), US4149996A(1975).
The catalyzer patent that to relate to tin be active ingredient: JP62126140A(1986), EP0228792A1(1986), US4766266A(1985), US3864284A(1973), US3641182A(1969), US3470262A(1966).
The catalyzer patent that relates to other active ingredient is as follows: US20100010280(2010), US20090321318(2009), US20090325784(2009), US20090325791A1(2009), USRE37663E(2002), US20010049461(2001), US6085145(2000), US6103103 (2000), US5736478(1998), US5593935(1997), US5559068(1996), US5476982(1995), US5401705(1995), US5276241(1994), US5346871(1994), US4070413(1978), US3980721(1976).But, the related catalyst activity metal component of these patents is not gold.
In addition, there are many open source literatures also to report the catalyzer of dehydrogenation of isobutane.As:
Open source literature Jilin Institute of Chemical Technology journal 1998(15) 4:18-21 has reported catalyst for preparing isobutene through dehydrogenation of iso-butane.The document is with Al 2o 3for carrier, take V as active ingredient, adopt conventional equi-volume impregnating Kaolinite Preparation of Catalyst.Temperature of reaction is that 520-620 ℃, air speed are 500-2000L*h -1carry out the dehydrogenation of isobutane reaction under condition.The evaluation of catalyzer is to carry out on fixed-bed reactor.
Open source literature Journal of Molecular Catalysis 2007(13) 5:373-377 has reported catalyst for preparing isobutene through dehydrogenation of iso-butane.The document is with Al 2o 3for carrier, take Cr as active ingredient, adopt conventional equi-volume impregnating Kaolinite Preparation of Catalyst.Reaction pressure is normal pressure, and temperature of reaction is that 580-640 ℃, air speed are 400h -1carry out the dehydrogenation of isobutane reaction under condition, the Trimethylmethane transformation efficiency is 60.1%, and selective isobutene is 93.2%.
Open source literature applied chemistry 1999(16) 4:111-113 has reported catalyst for preparing isobutene through dehydrogenation of iso-butane.The document is with Al 2o 3for carrier, take Pt, Sn, K is active ingredient, adopts the co-impregnation Kaolinite Preparation of Catalyst.Reaction pressure is normal pressure, and temperature of reaction is that 600 ℃, air speed are 2400-3600h -1carry out the dehydrogenation of isobutane reaction under condition, the Trimethylmethane transformation efficiency is 51.11%, and selective isobutene is 94.60%.
Open source literature applied chemistry 1999(16) 4:111-113 has reported catalyst for preparing isobutene through dehydrogenation of iso-butane.The document is with Al 2o 3for carrier, take Pt, Sn, K is active ingredient, adopts the co-impregnation Kaolinite Preparation of Catalyst.Reaction pressure is normal pressure, and temperature of reaction is that 600 ℃, air speed are 2400-3600h -1carry out the dehydrogenation of isobutane reaction under condition, the Trimethylmethane transformation efficiency is 51.11%, and selective isobutene is 94.60%.
Open source literature Journal of Molecular Catalysis 2007(Suppl) 21:701-702 has reported catalyst for preparing isobutene through dehydrogenation of iso-butane.The document is with Al 2o 3for carrier, take Ni, Ce as active ingredient, adopt solid reaction-directing agent method to take synthetic catalyst.Reaction pressure is normal pressure, and temperature of reaction is that 600 ℃, air speed are 1200h -1carry out the dehydrogenation of isobutane reaction under condition, the Trimethylmethane transformation efficiency is 15.1%, and selective isobutene is 70.5%.
Open source literature Fuel Process Tech92 (2011) 1632-1638 has reported catalyst for preparing isobutene through dehydrogenation of iso-butane.The document is with Al 2o 3for carrier, take Pt, Sn, K is active ingredient, adopts preparation catalyst.Reaction pressure is 0.1Mpa, and temperature of reaction is that 590 ℃, air speed are 3000h -1carry out the dehydrogenation of isobutane reaction under condition, the Trimethylmethane transformation efficiency is 29%, and selective isobutene is 94%.
Open source literature Industrial& Engineering Chemistry Research201150 (8): 4280-4285 has reported catalyst for preparing isobutene through dehydrogenation of iso-butane.The document is with Al 2o 3for carrier, take Pt, Sn, K, La is active ingredient, adopts preparation catalyst.Reaction pressure is 0.1Mpa, and temperature of reaction is that 590 ℃, air speed are 1500h -1carry out the dehydrogenation of isobutane reaction under condition, the Trimethylmethane transformation efficiency is 49%, and selective isobutene is 95%.
Open source literature Applied CatalysisA:General266 (2004) 229-233 has reported catalyst for preparing isobutene through dehydrogenation of iso-butane.The document is with ZnO-Cr 2o 3for carrier, take Pt, Sn as active ingredient, adopt preparation catalyst.Reaction pressure is normal pressure, and temperature of reaction is that 500 ℃, air speed are 2000h -1carry out the dehydrogenation of isobutane reaction under condition, the Trimethylmethane transformation efficiency is 49%, and selective isobutene is 94.9%.
Open source literature React.Kinet.Catal.Lett.Vol.74 (1) 103-110-2001 has reported catalyst for preparing isobutene through dehydrogenation of iso-butane.The document is with Al 2o 3for carrier, take V as active ingredient, adopt preparation catalyst.Reaction pressure is normal pressure, and temperature of reaction is that 590 ℃, air speed are 1000h -1carry out the dehydrogenation of isobutane reaction under condition, the Trimethylmethane transformation efficiency is 38.8%, and selective isobutene is 85.1%.
Open source literature React.Kinet.Catal.Lett.Vol.63 (1) 115-120-1998 has reported catalyst for preparing isobutene through dehydrogenation of iso-butane.The document is with SiO 2for carrier, take Rh, Sn as active ingredient, adopt preparation catalyst.Reaction pressure is normal pressure, and temperature of reaction is to carry out the dehydrogenation of isobutane reaction under 350 ℃ of conditions, and selective isobutene is 90%.
Open source literature Journal of Catalysis.157 (1995) 576-583 has reported catalyst for preparing isobutene through dehydrogenation of iso-butane.The document is with SiO 2for carrier, take Pt, Sn, K is active ingredient, adopts preparation catalyst.Reaction pressure is normal pressure, and air speed is 3.8h -1, temperature of reaction is to carry out the dehydrogenation of isobutane reaction under 400 ℃ of conditions, and the Trimethylmethane transformation efficiency is 4.5%, and selective isobutene is 99%.
In addition, the following discloses document has also been introduced the dehydrogenation of isobutane catalyzer.
To relate to platinum, tin be active ingredient the following discloses document: Chinese Journal of Catalysis2011(8) 32:1424-1429; Catalysis Today2011(1) 164:214-220; Korean Journal of Chemical Engineering2011(28) 2:370-377; Applied CatalysisA:General356 (2009) 88-89; Iran J Chem Chem Eng2009 (28) 1:23-30; Chemistry of fuel journal 2008(36) 2:197-201; Journal of Catalysis2007 (246) 1:158-165; Chemical Engineering Journal2006 (120) 1:25-32; Materials Letters2005 (59) 18:2319-2324; Journal of Catalysis2001 (1): 1-13; Langmuir2000(16) 13:5639-5643; Journal of Catalysis2000(192) 2:296-306; Applied chemistry 1999(16) 4:111-113; Applied Catalysis A-General1999 (189) 1:77-86; Reaction Kinetics and Catalysis Letters1999(66) 1:189-194; Chemical Engineering Science1996(51) 4:535-547; Applied Catalysis A-General1995 (129) 1:101-115; Journal of Catalysis1994(148) 2:771-778; Kinetics and Catalysis1986(27) 5:1112-1112.
What relate to chromium and be active ingredient has a following discloses document: Chinese Journal of catalysis2011(32) 8:1424-1429; Catalysis Today2011 (169) 1:-29-35; Journal of Molecular Catalysis 2007(Suppl) 21; Journal of Chim Phys Pcb1979(76) 5:458-464.
What relate to zinc and be active ingredient has a following discloses document: Applied Catalysis A-General2005 (292) 1:244-251.
What relate to palladium and be active ingredient has a following discloses document: Chinese Journal of catalysis2007(28) 2:124-130; Catalysis Today2005(104) 2-4:238-243; Catalysis Today2000(56) 1-3:35-44.
What relate to zinc and be active ingredient has a following discloses document: Catalysis Letters1998 (55): 173-176, Journal of Japan Petroleum Institute2002 (45) 3:150-155; SCI 1998(19) 1:116-119; Journal of Catalysis1996(161) 2:730-741.
What relate to chromium and be active ingredient has a following discloses document: catalysis journal 2011(32) 8:1424-1429; Applied Catalysis A-General2010 (382) 2:139-147; Applied Catalysis A-General2004 (258) 2:153-158; Catalysis Letters2002(87) 3-4:273-279; Chemical Engineering and Processing2002(41) 4:337-347; Journal of Molecular Catalysis 1999(13) 5:374-376; .
What relate to iron and be active ingredient has a following discloses document: Chemical Communications:2003(14): 1764-1765.
What relate to nickel and be active ingredient has a following discloses document: Reaction Kinetics and Catalysis Letters2010(101) 1:173-181; Applied Catalysis A-General2010 (375) 2:272-278; Journal of Molecular Catalysis A:2010(315) 2:221-225; Chemical Communications2009(17): 2376-2378; Kinetics and Catalysis2009(50) 4:577-582; Applied CatalysisA-General2003 (250) 1:143-150; Applied Catalysis A-General2002 (232) 1-2:189-202; Journal of Catalysis1994(146) 1:40-55; Chemistry and Technology ofFuels and Oils1988(24) 1-2:49-52.
What relate to other active ingredient has a following discloses document: Catalysis Today2011 (164) 1:347-352; The journal 2010(29 of Dalian Polytechnic University) 3:179-181; Journal of Catalysis2009(267) 2:158-166; Journal of the American Chemical Society2009(131) 22:7735-7741; Applied Catalysis A-General2009 (354) 1-2:72-81; Applied Catalysis A-General2009 (355) 1-2:192-201; Catalysis Letters2008(126) 3-4:293-300; Catalysis journal 2007(33) 2:124-130; Industrial Catalysis 2007(15) 9:30-32; Reaction Kinetics and Catalysis Letters2007(92) 2:267-274; Applied Catalysis A-General2007 (333) 1:30-41; Kinetics and Catalysis2007(48) 2:255-264; Applied Catalysis A-General2006 (311): 51-57; Catalysis Letters2006(88) 2:293-300; Catalysis Letters2006(111) 1-2:79-85; Journal of Catalysis1998(179) 2:459-468; Journal of Molecular CatalysisA:2004(218) 2:179-186; Chemical Engineering Journal2003(95) 1-3:37-45; SCI 2002(23) 5:857-860; Reaction Kinetics and Catalysis Letters2002(75) 1:31-37; Reaction Kinetics and Catalysis Letters2001(74) 1:103-110; Kinetics and Catalysis2001(42) 6:821-827; Catalysis Today2000 (61) 1-4:377-382; Catalysis Letters2000(69) 1-2:65-70; Applied Catalysis A-General1998 (170) 1:23-31; Applied Catalysis A-General1998 (168) 2:243-250; Industrial& Engineering Chemistry Reasearch1997(36) 11:4821-4826; Applied chemistry 1994(11) 4:117-119.But all do not relate to golden use in these documents.
Two, Trimethylmethane catalytic pyrolysis preparing ethylene and propylene.
Patent CN200510002414.9(2005) disclosed a kind of method that improves ZSM-5 type zeolite molecular sieve activity by modification in.Its technical characteristics is: the ZSM-5 type zeolite molecular sieve that is first 10-200 to silica alumina ratio carries out acid treatment and obtains the Hydrogen ZSM-5 zeolite, and then to its loaded metal chromium, iron, zinc or silver.This is actually catalyzer is carried out to the multi-step processing.The peak optimization reaction result of the catalyzer made by the method is: in the situation that take Trimethylmethane as reaction raw materials, in the temperature range of 500 ℃-625 ℃, the Trimethylmethane transformation efficiency is increased to 99% from 10%, and the triolefin molar yield is increased to 65.63% from 11.42%.625 ℃ of temperature, gas phase air speed 12000h -1, hydrogen is as carrier gas, under the condition that the unstripped gas volumetric concentration is 20%, and triolefin molar yield 65.62%, Trimethylmethane transformation efficiency 99.07%.But this reaction wants to obtain the Trimethylmethane transformation efficiency of 90% left and right need to be in reaction more than 600 ℃.This catalyst activity is lower, and under harsh reaction conditions, energy consumption is high, catalyst deactivation speed is accelerated.
Patent CN200410097691.8(2004) disclosed a kind of method of butane producing olefin hydrocarbon by catalytic pyrolysis in.Its technical characteristics is: the ZSM-23 molecular screen that the employing silica alumina ratio is 30-300 is as catalyzer, (55% normal butane and 45% Trimethylmethane are as reactant to using mixed c 4 alkane, nitrogen is carrier gas, 500-650 ℃ of reaction, within 10-600 minute, carries out catalytic cracking reaction.Temperature of reaction is when 500 ℃ of-650 ℃ of scopes, and the butane total conversion rate is increased to 87.4% from 43.5%, illustrates that this catalyzer just has under hot conditions active preferably.Can obtain the highest total butanes conversion 87.4% under 650 ℃ of conditions, dry gas by product selectivity 34.9%, propane selectivity 6.3%, triolefin overall selectivity (ethene, propylene, butylene) 45%, other selectivity of product 17%.Can find out, this reaction occurs under hot conditions, and the reaction of serious carbon distribution can occur catalyzer, and deactivation rate is accelerated, and the growing amount of dry gas by product increases again, has reduced the effective rate of utilization of raw material.
Patent CN98804586.9(1998) method for preparing catalyst of a kind of non-aromatics preparing aromatic hydrocarbon and alkene and the application in paraffin conversion thereof have been disclosed in.Its technical characteristics is: the MFI zeolite that the silica alumina ratio of take is 12-100 is carrier, using zinc as the first metal, at least one of usining in Ti, Cr, Mo, B, Si and P as second or secondary metal come bimetal to help catalysis, the weight percent of zinc in the acid treatment zeolite of dipping is 0.1-6wt%, the weight percent 0.2-12wt% of secondary metal in the acid treatment zeolite of dipping.The peak optimization reaction result of the catalyzer made by the method is: with the gasoline gold-plating journey raw material of refinery catalytic cracking unit, react on the catalyzer obtained in above-mentioned preparation method, with the flow of about 14ml/h, under 600 ℃ and normal atmosphere, by reactor, can obtain the highest 45% aromatics yield and 23% olefin yields.But the method be take and mainly produced aromatic hydrocarbons as main, olefin yields is lower, severe reaction conditions and do not mention the conversion situation of butane as raw material.
Patent CN98125043.2(1998) disclose a kind of low-carbon alkanes in and produced the preparation method of alkene catalyst.Its technical characteristics is: adopt a kind of element be selected among basic metal, alkaline-earth metal or VIII group 4 transition metal to carry out modification to the supersiliceous zeolite molecular sieve of the five-membered ring structure containing rare earth and phosphorus.Wherein, the silica alumina ratio of zeolite is 40-80, and phosphorus content is (with P 2o 5meter) 2.5-5.0wt%, rare earth is (with Re 2o 3meter) 20.8wt%.Preferred modified metal is K, Ba, Fe, Ni, and preferred content (take metal oxide) is 0.4-2.5wt%.In the situation that using Skellysolve A as reaction raw materials, reacting on fixed-bed micro-reactor continuously, at 550 ℃ of temperature of reaction, weight space velocity 56.8h -1condition under obtained 72.38% feed stock conversion, 47.18% C2 =-C4 =selectivity, this catalyst activity is lower, and under 550 ℃ of conditions, Skellysolve A transformation efficiency and olefine selective are lower, do not mention the situation of selective conversion Trimethylmethane in this patent simultaneously.
Open source literature Catalysis Cammunications6 (2005) 297-300 has reported ZSM-23 impact on the butane catalytic cracking reaction as catalyzer, its technical characteristics is: using the Trimethylmethane of 55% normal butane and 45% as raw material, on the ZSM-23 catalyzer that is 30,60,100 at silica alumina ratio, react, reaction conditions is, nitrogen is as carrier gas, and the gas phase air speed is 3000mlgh -1, temperature of reaction is 600 ℃, pressure is normal pressure.Result shows, along with the raising of catalyzer silica alumina ratio, the transformation efficiency of butane reduces, and product yield raises.On the catalyzer that is 30 at silica alumina ratio, reaction is 20 hours, 41.9% yield of ethene and 14.1% propene yield have been obtained, but, this temperature of reaction is high, the less stable of catalyzer, under the temperature of reaction of 600 ℃, after reacting 70 hours, transformation efficiency is down to 70% by 88%, the total recovery of ethene and propylene is down to 20% by 50%, and this catalyst deactivation speed is unfavorable for the stability of reacting.
Open source literature Catalysis Cammunications6 (2005) 297-300 has reported that use trace iron element is molecular sieve modified to the HZSM-5 type, has obtained ethene, propylene and butylene selectivity preferably.Its technical characteristics is: using pure Trimethylmethane as reaction raw materials, ZSM-5(silica alumina ratio in the modification of trace iron element dipping is 32) to react on the type zeolite molecular sieve, the iron ion charge capacity is respectively 0.010,0.021,0.041,0.083,0.165,0.248 and 0.331mmol/g.Using nitrogen as carrier gas, and all catalyst performance contrast experiments carry out at 600 ℃ of temperature of reaction and 625 ℃ of two temperature.Its optimal result is: the molecular sieve of 0.010mmol/g Fe modification is at 625 ℃, under the reaction conditions of normal pressure, and Trimethylmethane transformation efficiency 99.1%, dry gas by product selectivity 15.2%, triolefin selectivity 65.6%, propane selectivity 2.3%, arenes selectivity 16%.But this catalyst activity is lower, Trimethylmethane transforms need to carry out under hot conditions fully, and energy consumption is high, catalyst deactivation is fast.
Open source literature Catalysis Cammunications7 (2006) 199-203 has reported that use trace chromium element is molecular sieve modified to the HZSM-5 type, ethene and Propylene Selectivity have preferably been obtained, its technical characteristics is: using pure Trimethylmethane as reaction raw materials, ZSM-5(silica alumina ratio in the modification of trace chromium element dipping is 32) to react on the type zeolite molecular sieve, the chromium ion charge capacity is respectively 0.004,0.010,0.019,0.038,0.077,0.154 and 0.231mmol/g.Nitrogen is as carrier gas, and all catalyst performance contrast experiments carry out at 600 ℃ of temperature of reaction and 625 ℃ of two temperature.Its optimal result is: the molecular sieve of 0.040mmol/gCr modification is at 625 ℃, under the reaction conditions of normal pressure, and Trimethylmethane transformation efficiency 99.7%, dry gas by product selectivity 16.4%, triolefin selectivity 61%, propane selectivity 2.9%, arenes selectivity 19%.But this catalyst activity is lower, Trimethylmethane transforms need to carry out under hot conditions fully, and energy consumption is high, catalyst deactivation is fast.
Open source literature Porous Mater (2008) 15:213-220 has reported the impact of catalyzer silica alumina ratio on the Trimethylmethane catalytic cracking reaction, its technical characteristics is: using pure Trimethylmethane as reaction raw materials, nitrogen is as carrier gas, on the FeHZSM-5 of Different Silicon aluminum ratio, CrHZSM-5 catalyzer, (silica alumina ratio is 25,38,50,80 and 150) reaction, when the silica alumina ratio of catalyst Precursors is increased to more than 50, the selectivity of ethene and propylene obviously raises, and the transformation efficiency of Trimethylmethane reduces.
Open source literature Applied CatalysisA:General340(2008) 176-182 has reported the impact of phosphorous modified ZSM-5 catalyst on the butane cracking reaction, its technical characteristics is: adopting the ZSM-5(silica alumina ratio after the modification of phosphorus dipping is 25) zeolite molecular sieve is as catalyzer, and the phosphonium ion charge capacity is respectively 0.1,0.5,1,3,6wt%.With mixed butanes (50% normal butane, 50% Trimethylmethane) as raw material, all catalyst performance contrast experiments carry out its optimal result at 600 ℃ of temperature of reaction and 650 ℃ of two temperature, the molecular sieve of 0.5wt%P modification is at 650 ℃, under the reaction conditions of normal pressure, and Trimethylmethane transformation efficiency 99.3%, dry gas by product selectivity 21.4%, triolefin selectivity 55.7%, propane selectivity 1.9%, arenes selectivity 15.6%.But this reaction needed is carried out under hot conditions, energy consumption is higher, and dry gas by product selectivity is larger, and after reaction 10.5 hours, the total conversion rate of butane drops to 87.3% by 99.6%, the less stable of this explanation catalyzer.
In reported catalyst research, the metal component of load mainly concentrates on Zn, Fe, P, and Cr, Ag, Ni, Ce, La etc., do not have report for the catalytic pyrolysis of Trimethylmethane and take Au as active ingredient.
The preparation of nano catalyst and application are the great discoveries of catalysis circle.Always gold is considered to catalytically inactive, but, after it is loaded on oxide carrier and to carry out high dispersive, just demonstrates unique catalytic activity.Nano catalyst is at catalysis CO oxidation, ozone decomposed, water gas shift reaction, NO xreduction, acetylene hydrochlorination, epoxidation of propylene, fuel cell, field of petrochemical industry demonstrate application prospect (Catal.Rev.-Sci.Eng, 1999,41 (3) 319-388).
The preparation method of nano catalyst is divided into two kinds: the one, and carrier and golden precursor coprecipitation method; The one, golden precursor is loaded to pickling process and deposition-precipitation method on the carrier prepared in advance.The preparation method of early stage load type gold catalyst pickling process commonly used.It is lower that pickling process is generally used for preparing active component content, and need the catalyzer of sufficient mechanical strength.By the preparation process of the method nano catalyst, be, at first by carrier impregnation in containing in golden salts solution, and then carry out drying, roasting and reduction processing, method is simple.It is carrier that pickling process can be selected various metal or nonmetal oxide and molecular sieve etc.The commonly used golden precursor for preparing nano catalyst is hydrochloro-auric acid (HAuCl 4.3H 2o) and gold trichloride (AuCl 3) and gold complex KAu (CN) 2[Au (en) 2] Cl 3(en is quadrol) etc.
Coprecipitation method is the effective ways of preparation high capacity amount Au catalyst, typical preparation process is: the precursor salt solution of carrier is mixed with golden precursor salt solution, then precipitated with precipitation agent, then carry out standing, filtration, washing, drying and high-temperature roasting and process.The advantage of coprecipitation method is that preparation is reproducible, and shortcoming is that the part gold grain can be buried in carrier inside, and the utilization ratio of gold is low, is not suitable for the carriers such as titanium oxide, zeolite molecular sieve.When the application precipitator method, the control of pH value is technological difficulties.
Deposition-the precipitator method are also supported catalyst preparation methods commonly used, and it has the advantage of pickling process and the precipitator method concurrently.The canonical process for preparing Au catalyst by the deposition-precipitator method is: by metal or nonmetal oxide and molecular sieve etc. in carrier joins golden precursor solution, under certain temperature of reaction, continuously stirring also dropwise adds precipitation agent, solution reaction is carried out under suitable pH value, until precipitation fully.And then solid substance is carried out to sedimentation, filtration, washing, drying, roasting or activation treatment.
As a rule, after the load gold catalyst drying of the preparation that ins all sorts of ways, with+3 valency oxidation state forms, exist, after high-temperature heat treatment, most gold atoms become zeroth order.In order to make load gold catalyst have high reactivity, it is crucial adopting suitable preparation method to make gold particle high dispersive on carrier.
Now, existing many patents have disclosed the preparation method of load type nano gold catalyst.As:
Patent CN101530814A(2009) disclosed a kind of preparation method of load type nano gold catalyst.It is characterized in that: the HTS with mesoporous-micropore composite structure of take is carrier, and carrying method is deposition-precipitation method, loads under normal pressure and carries out, and take hydrochloro-auric acid as golden presoma.
Patent CN101237931A (2008) has disclosed a kind of preparation method of load gold catalyst.It is characterized in that: take porous metal oxide as carrier, hydrochloro-auric acid is presoma, and carrying method is conventional pickling process, is immersed under normal pressure and carries out.
Patent CN101204655A(2008) disclosed a kind of preparation method of nano catalyst.It is characterized in that: with aluminum oxide, silicon oxide, pottery, TiO 2deng being carrier, hydrochloro-auric acid is golden presoma, and carrying method is pickling process, is immersed under the condition that ultrasonic wave or ultrasonic wave and vacuum coexist and carries out.
Patent CN1795985A (2006) has disclosed a kind of method for preparing load type gold catalyst.It is characterized in that: take iron nitrate as the co-precipitation carrier, the chloric acid gold is presoma, take sodium carbonate as precipitation agent, and carrying method is coprecipitation method, and co-precipitation is carried out under normal pressure.
Patent CN1565727A(2005) disclosed a kind of preparation method of load type nano gold catalyst.It is characterized in that: with SiO 2, Al 2o 3, TiO 2deng oxide compound, be carrier, the chloric acid gold is presoma, and carrying method is pickling process, and dipping carries out under normal pressure in isopyknic mode.
Following patent has also disclosed the preparation method of load type gold catalyst.
Relate to SiO 2carrier loaded Au catalyst has following patent: CN101797514A (2010), CN101862660A (2010), CN101574654A(2009), US6821923 (2004), EP1044067B1 (2004), EP1027153B1 (2004), US6486093 (2002), US6303537 (2001), US6174531 (2001), EP0906151B1 (2001), US6114571 (2000), CN1251323A (2000), WO030818A1 (1999), WO062633A1 (1999), WO062632A1 (1999), US5693586 (1997).
Relate to Al 2o 3the load gold catalyst of carrier has following patent: CN101618328A (2010), US0010278A1 (2010), EP1309536B1 (2010), US0221849A1 (2009), US0088319A1 (2009), CN101147862A (2008), CN101049561A (2007), CN101036887A (2007), WO065138A1 (2006), US7119225 (2006), CN1827213A (2006), WO016298A1 (2002), EP0909213B1 (2001), EP0653401B1 (1997).
Relate to TiO 2the load gold catalyst of carrier has following patent: CN101711982A (2010), EP1309536B1 (2010), CN101380575A (2009), WO076137A3R4 (2008), WO003450A1 (2006), US7119225 (2006), US6821923 (2004), WO016298A1 (2002), CN1349430A (2002).
Relate to ZrO 2the load gold catalyst of carrier has following patent: US0190347A1 (2007), WO0465145 (2006), US0276741A1 (2005), WO046255A1 (1999), US5895772 (1999).
In addition, patent CN101683619A (2009) relates to Fe 2o 3load gold catalyst for carrier.
Patent CN101722009A (2010) relates to take the load gold catalyst that CuO is carrier.
The load gold catalyst that relates to composite oxide carrier has following patent: CN101822990A (2010), CN101822981A (2010), CN101612578A (2009), CN101376107A (2009), US02410381A1 (2008), US0193354A1 (2008), CN1724153A (2006), US0065355A1 (2005), CN1698932A (2005), US0127353A1 (2004), US0060643A1 (2003), USP4839327, USP4837219.
The load gold catalyst patent that relates in addition carbon support: CN101631610A (2010), CN101648137A (2010), CN101785997A (2010), CN101804347A (2010), CN101829567A (2010).
But existing patent all prepares load gold catalyst by non-pressure process.
In addition, many open source literatures have also related to the preparation method of load type nano gold catalyst.As:
Open source literature Appl.Catal.A:Gen.291 (2005) 62, J.Catal.231 (2005) 105 and Geochem.Intern.11 (1985) 1656 have reported that acidity (pH) prepares the impact of load type gold catalyst on deposition-precipitation method, and carrier is TiO 2.Result shows, pH has considerable influence to the activity of nano catalyst.This be mainly because, under different pH values, the hydrolysis degree difference of golden precursor compound.Along with the rising of pH value, golden precursor compound (AuCl 4) -progressively be hydrolyzed to AuCl 3(H 2o), (AuCl 3(OH)) -, (AuCl 2(OH) 2) -, (AuCl (OH) 3) -(Au (OH) 4) -.
Different golden presomas are hydrolyzed to because of nature differences such as adsorptive poweies, and load gold catalyst is exerted an influence.The deposition-precipitation method that the disclosure document adopts carries out under condition of normal pressure.
Open source literature Appl Catal A:Gen, 291 (2005) 162 have reported a kind of method for preparing load gold catalyst.Its technical characterictic is: take Y, β and mordenite as carrier, with HAuCl 4for golden presoma, with NaOH, be precipitation agent, adopt deposition-precipitation method, operate under normal pressure and carry out.
Open source literature Appl Catal B:Env, 41 (2003) 83 have reported a kind of method for preparing load gold catalyst.Its technical characterictic is: take Y, β and mordenite as carrier, with HAuCl 4for golden presoma, with NaOH, be precipitation agent, adopt deposition-precipitation method, operate under normal pressure and carry out.
Open source literature Appl.Catal.A:Gen.240 (2003) 243 has reported a kind of method for preparing load gold catalyst.Its technical characterictic is: take Ti-MCM-41 as carrier, take NaOH as precipitation agent, adopt deposition-precipitation method, operate under normal pressure and carry out.
Open source literature J.Catal.209 (2002) 331 has reported a kind of method of load gold catalyst.Its technical characterictic is: take Ti-MCM-48 as carrier, take NaOH as precipitation agent, adopt deposition-precipitation method, operate under normal pressure and carry out.
Open source literature Appl.Cattal.A:Gen.226 (2002) has 1. reported that deposition-precipitation method prepares the principles of chemistry of nano catalyst.Precipitation agent is urea, TiO 2for carrier.The disclosure document adopts TiO 2for carrier and urea are precipitation agent, deposition-precipitation method, operate under condition of normal pressure and carry out.
Open source literature App.Catal.A:Gen.190 (2000) 43 has reported a kind of method for preparing load gold catalyst.Its technical characterictic is: take Ti-MCM-41 as carrier, take NaOH as precipitation agent, adopt deposition-precipitation method, operate under normal pressure and carry out.
In addition, the following discloses document also relates to the preparation method of load type gold catalyst: J.Catal, 2006,237:303-313; Catal.Today, 2006,111 (1-2): 22-33; J.Phys.Chem, B:2005,109:2321-2330; Catal.Lett, 2005,99 (3-4): 235-239; J.PhysChem, B:2005,109:3956-3965; Appl.Catal; B:Environ; 2005,61:201-207; Appl.Catal, A:Gen, 2005,191:222-229; Appl.Catal.A:Gen, 2004,267:191-201; Appl.Catal, A:Gen, 2004,277:31-40; J.Am.Chem.Soc, 2004,126:38-39; J.Catal, 2004,226:156-170; J.Catal, 2003,216 (1-2): 213-222; Catal.Lett, 2003,86:1-8; Oxid.Commun, 2003,26 (4): 492; Appl.Catal, A:Gen, 2003,246:29-38; Appl.Catal, A:Gen, 2003,243:25-33; Appl.Catal.A:Gen., 2002,226:1-13; Appl.Catal, A:Gen, 226 (2002) 1; Chemical progress 2002 (5): 360-367.J.Phys.Chem, J.Catal, 2002,209:331-340; B:2002,106 (31): 7634-7642; Catal.Today, 2002,74:265-269; Gold Bull, 34 (2001) 4:11; Appl.Catal, A:Gen, 2001,215:137-148; Appl.Catal, A:Gen, 2001,209:291-300; Catal.Today, 2001,64 (1): 69-81; Appl.Catal, B:Environ, 2001,33:217-222; Appl.Catal, A:Gen, 2001,222:427-437; Appl.Catal, B:Environ, 2000,28:245-251; J.Phys.Chem, B:2000,104:11153-11156; J.Catal, 2000,191:332-347; J.Catal, 2000,191:430-437; Catal.Rev-Sci.Eng, 1999,41 (3): 319-388; Catal.Today, 1999,54:31-38; Gold.Bull, 1998,31:105-106; Gold Bull, 31 (1998) 4:111-118; J.Catal, 1998,178:566-575; Catal.Lett. (1997) 43 (1-2): 51-54; Catal.Today, 36 (1997) 153; Catal.Today, 1996,29:443-447; Surf.Sci.Catal, 91 (1995) 227; " Preparation of catalysts V " Edit., 1991, Amsterdam, 695-704; J.Catal., 1989,115:301-309; Stud.Surf.Sci.Catal, 44 (1988) 33; Chem.Lett, 2 (1987) 405; J.Chem.Soc.Faraday Trans, 175 (1979) 385.
Above open source literature has adopted different methods and different oxide compound and zeolite molecular sieve carrier to prepare load gold catalyst.But the common feature of these methods is that during load, operation is all carried out under normal pressure.Prepared catalyzer is easy to reunite through roasting.When adopting ZSM-5 to be carrier, can only obtain the load type gold catalyst that gold grain is 40-50nm, can not obtain more short grained Au/ZSM-5 catalyzer.
The present invention utilizes the negative pressure deposition-precipitator method to prepare load type gold catalyst, has that metal dispersity is high, the treatment time is short and characteristics such as saboteur's sieve skeleton shelf structure not.We are through the research discovery, and catalyzer prepared by the negative pressure deposition-precipitator method can improve the dispersity of gold on carrier, especially improve the degree of uniformity and the granularity that has reduced gold grain of gold grain.Therefore, the catalyzer prepared by the method, as the novel supported Au catalyst of Trimethylmethane catalytic pyrolysis, has reactive behavior high, and stability and selectivity are good, and have unique acidity, non-corrosiveness and environmental pollution, is easy to the characteristics of preparation and regeneration.
Summary of the invention
The invention provides the method for a kind of modified molecular sieve catalyst for the Trimethylmethane catalytic pyrolysis.Core of the present invention is to make the first dehydrogenation of Trimethylmethane become iso-butylene, and then make iso-butylene according to the carbonium ion reaction mechanism carry out polymerization, scission reaction obtains split product.The main purpose product comprises ethene, propylene, iso-butylene and BTX aromatics, and these products can be regulated by changing reaction conditions according to the variation of the market requirement.We find, the dehydrogenation and cracking of Trimethylmethane should be used metal-sour dual-function catalyst.
1.C 4H 10→C 4H 8+H 2
2.C 4H 10→C 3H 6+CH 4
3.2C 4H 8→C 8H 16
4.C 8H 16→C 5H 10+C 3H 6
5.C 5H 10→C 2H 4+C 3H 6
Wherein, the dehydrogenation reaction that the first reactivation process of Trimethylmethane is reaction 1 under catalyst acid central role generates butylene and hydrogen generates propylene and methane with the demethylating reaction that reacts 2, by the butylene intermediate that reacts 1 generation, the polymerization scission reaction further occurs on the acid site of catalyzer and generates C 2 =-C 8 =.Reaction 1 and 2 is to occur under the activation in the acid site of catalyzer, the generation of reaction 2 can cause the generation of a large amount of methane and then reduce the effective rate of utilization of raw material, therefore, the Efficient Conversion of realizing Trimethylmethane needs catalyzer to have the activation temperature that suitable strength of acid reduces Trimethylmethane to reach the purpose that reduces the dry gas by product, improve the selectivity of reaction 1 simultaneously, make the first dehydrogenation of Trimethylmethane generate after iso-butylene the effect by acid site again and generate cleavage reaction product.
While being carried on supersiliceous zeolite by present method by nanometer gold, gold can with supersiliceous zeolite generation strong interaction, thereby form the nm gold particles of high dispersive.And due to the polarized action of Au, forming process acid when Au and carrier function.Also there is metallicity by the gold of load simultaneously, thereby formed metal-sour dual-function catalyst.We find by research; the carrying method of Au is very important; after molecular sieve is carried out to sufficient negative pressure degasification purifying treatment; adopt the negative pressure deposition-precipitation method that golden precursor is loaded on molecular sieve carrier, then under gas shield, calcination process can obtain high-dispersion loading type Au catalyst as above again.During due to negative pressure deposition-precipitation method gold-supported, following chemical reaction can occur: 1. HAuCl 4dissolve in water and can hydrolysis generate hydroxy chloride-Jin (III) anion complex [Au (OH) xcl 4-x] -.In the time of between the pH of solution value is controlled at 5～8, hydroxy chloride-Jin (III) anion complex is mainly with [Au (OH) 2cl 2] -[Au (OH) 3cl] -monomeric form exists.2. when take urea as precipitation agent, temperature of reaction is during higher than 60 ℃, CO (NH 2) 2+ 3H 2o → CO 2+ 2NH 4 ++ 2OH -; NH 4 ++ OH- -→ NH 4oH; NH 4oH → NH 3+ H 2o.So, in the process with the deposition-precipitation method Kaolinite Preparation of Catalyst under negative pressure, because constantly vacuumizing, make the CO produced in reaction process 2, NH 3, the gas such as HCl is pumped, and the pH value is remained in the scope of optimum gold-supported.Prepare load gold catalyst with deposition-precipitation method and also help purification molecular sieve internal surface and duct under condition of negative pressure, make Au be easy to enter in molecular sieve pore passage.Be conducive to gold complex in molecular sieve surface high dispersive and strong interaction occurs.
We also prevent that by introducing the second metal gold particle from assembling when the roasting.The second metal added plays promoting catalysis simultaneously.Said molecular sieve refers to the supersiliceous zeolite molecular sieve, especially S-1, ZSM-5, ZSM-8, ZSM-11, MCM-22, MCM-49, MCM-56, ITQ-2, and ZSM-12, beta-zeolite, mordenite and TS-1 molecular sieve or the above-mentioned zeolite that process is metal-modified and additive method was processed.Said golden precursor mainly refers to HAuCl 4, precipitation agent mainly refers to urea.If the second master metal Zn, Fe, Mo, Ni, Ga, Co, Pt, Pd, Ag or Cu.
Load type gold catalyst by this invention preparation has the required acid site of Trimethylmethane catalytic pyrolysis and metal active center, can make Trimethylmethane under the difunctional effect of metal and acid, dehydrogenation generates alkene, alkene obtains proton and forms carbonium ion on acid site, and carbonium ion carries out the polymerization cracking again and generates corresponding alkene.
Technical scheme of the present invention is as follows:
1. the preparation of load gold catalyst
The first step, carry out pre-treatment to the supersiliceous zeolite carrier.
(1). the zeolite that the silica alumina ratio of said supersiliceous zeolite is 10～∞, as ZSM-5, ZSM-8, ZSM-11, MCM-22, MCM-49, MCM-56, ITQ-2 and ZSM-12, beta-zeolite, mordenite, TS-1 and pure silicon zeolite or through above-mentioned zeolite metal-modified and that additive method was processed.The grain fineness number of zeolite is between 5nm ~ 30 μ m.The supersiliceous zeolite carrier is carried out to calcination process.Maturing temperature selects 300 ~ 700 ° of C, preferably 400 ~ 600 ° of C; Roasting time is 4 ~ 20 hours, preferably 3 ~ 8 hours.
Above carrier synthetic can adopt the formula in disclosed patent and document to carry out.As patent US3702886(1972), US3941871(1976), US4061724(1977), US4166099(1979), CN1086792A(1994), CN1219571A(1999), CN1056818C(2000), CN100457622A (2001), WO0138224A(2001), CN1212892A (2002), CN1328960A(2002), CN1088406C(2002), CN1417116A(2003), CN1530323A(2004), CN1699173A(2005), CN1686801A(2005), CN100344375A (2005), CN1715186A(2006), CN101007637A(2007), CN1307102C(2007), CN101279746A(2008), CN101214971(2008), CN101613114(2009), CN101554592A(2009), CN101559955A(2009), CN101428818B(2010), CN101993091A(2011) CN101417810A (2009), CN101468800 (2009), CN101519216 (2009), CN101554592A (2009), CN101618337A (2010), US20100298598A1 (2010), CN101801848A(2010), CN10204023A(2010), CN101973560A(2011), US7883686B2 (2011), WO2011061204A1 (2011), Microporous and Mesoporous Materials31 (1999) 241-251, Journal of Materials Chemistry 12 (2002) 369 – 373, Journal of Molecular Catalysis B:Enzymatic22 (2003) 119-133, Journal of Catalysis 255 (2008) 68-78.The slip-stick artist who is familiar with this area all can adopt the technological method of reporting in existing open source literature and patent, carries out the synthetic of carrier.
(2). the ammonium exchange is processed: baked molecular sieve is carried out to ion exchange treatment with ammonium salt solution at suitable temperature.Then, use deionized water wash, drier, roasting obtains hydrogen type catalyst.Ammonium exchange process major control Na +content, make it higher than 1.0%, not be preferably lower than 0.8%.Any in the optional ammonium nitrate of described ammonium salt, ammonium chloride, volatile salt etc., ammonium salt solution concentration is 0.05 ~ 1.0mol/L, the liquid-solid volume ratio of catalyzer and ammonium salt solution is 1:1 ~ 20:1, preferably 3:1 ~ 10:1; Exchange temperature is 20 ~ 80 ° of C, preferably 20 ~ 60 ° of C; Be 0.2 ~ 100 hour swap time, preferably 0.5 ~ 4 hour; Exchange times 1 ~ 5 time.80 ~ 200 ° of C of drying temperature, 1 ~ 100 hour time of drying; Due to NH 4 +nH 3+ H +middle NH 3with proton H +between strong complexing power, require roasting process to need fully, so maturing temperature selects 300 ~ 700 ° of C, preferred 400 ~ 600 ° of C; Roasting time is 4 ~ 20 hours, preferably 3 ~ 8 hours.Said Na +the measuring method of content can adopt flame photometer, Inductively Coupled Plasma(ICP) measured.The slip-stick artist who is familiar with this area can carry out Na with reference to specification sheets +measure.
(3). sour reaming is processed: hydrogen type catalyst is carried out at suitable acid concentration and temperature to sour reaming processing.Then extremely neutral with deionized water wash, drier, roasting obtains catalyzer.The optional HCl of said acid, HNO 3, H 2sO 4or any in citric acid, preferably HNO 3and citric acid.Because adopt HCl can introduce Cl -, and H 2sO 4decompose difficulty, be difficult for removing.Acid concentration is 0.05 ~ 6mol/L, the liquid-solid volume ratio 1:1 of acid solution and catalyzer ~ 20:1, preferably 3:1 ~ 10:1; The acid reaming treatment time is 30min ~ 100 hour, preferably 1 ~ 5 hour; Treatment temp is 20 ~ 80 ° of C.Drying temperature is 50 ~ 200 ° of C, and be 3 ~ 20 hours time of drying, and maturing temperature selects 300 ~ 600 ° of C, and roasting time is 1 ~ 4 hour.
The purpose of acid reaming is to remove the unformed impurity of HZSM-5 nucleus inside, increases the rate of diffusion in duct.In fact the hydrogen type catalyst obtained after the ammonium exchange just can directly be used as catalyzer.But sour reaming is to being conducive to improve the activity of catalyzer.
Second step adopts deposition-precipitation method to prepare load gold catalyst under condition of negative pressure.
(1). with negative pressure deposition-precipitation method gold-supported: will carry out the negative pressure degasification purifying treatment under certain temperature through pretreated Hydrogen supersiliceous zeolite carrier.Then under fully stirring, first use golden precursor solution contact carrier, and then add precipitation agent to pass through negative pressure deposition sedimentation reaction load gold in mixture.The negative pressure degasification treatment temp is 20～90 ℃, and the degassed time is 0.5～20 hour, range of negative pressure is-0.01～-0.1MPa.Although higher vacuum tightness is favourable to purifying, can increase the catalyzer cost of manufacture.Said golden precursor is HAuCl 4, said precipitation agent is urea.Wherein, HAuCl 4suitable concentration be 5～50mmol/L, the Optimum of urea is 3～10g, the volume ratio of golden precursor solution and molecular sieve carrier is 1:1～1:10, pH is 4～9, optional 20～95 ℃ of deposition sedimentation temperature of reaction, optional 5～100 hours of churning time.
(4). the throw out to gold-supported carries out aftertreatment: comprise solid-liquid separation, with deionized water wash to without Cl -, and drying and the roasting of solid substance.Wherein, optional 80～200 ℃ of drying temperature, optional 0.5～100 hour of time of drying.The optional electrical heater of the roasting of catalyzer (retort furnace) roasting, also can select the plasma body roasting, optional 200 ℃～600 ℃ of maturing temperature, optional 0.5～100 hour of roasting time, the optional air of calcination atmosphere, nitrogen, helium, argon gas and oxygen.
The 3rd step, adopt pickling process load the second active ingredient.
(1). with pickling process load the second metal: the load type gold catalyst that will prepare through the negative pressure deposition-precipitation method carries out the negative pressure degasification purifying treatment at a certain temperature.Then under fully stirring, by pickling process load the second metal.The negative pressure degasification treatment temp is 20～90 ℃, and the degassed time is 0.5～20 hour, pressure range be normal pressure～-0.1MPa.Although higher vacuum tightness is favourable to purifying, can increase the catalyzer cost of manufacture.Said the second metal is Zn, Fe, Mo, Ni, Ga, Co, Pt, Pd, Ag or Cu.The second preferred metal is introduced with nitrate, also available chlorate, and suitable concentration is 5～50mol/L, the volume ratio of metallic precursor solution and molecular sieve carrier is 1:1～1:10, optional 20～95 ℃ of dipping temperature, optional 1～100 hour of churning time.
(2) solid substance is carried out to aftertreatment: comprise solid-liquid separation, and the drying of solid substance and roasting.Wherein, optional 80～200 ℃ of drying temperature, optional 0.5～100 hour of time of drying.The optional electrical heater of the roasting of catalyzer (retort furnace) roasting, also optional plasma body roasting, optional 200 ℃～600 ℃ of maturing temperature, optional 0.5～100 hour of roasting time, the optional air of calcination atmosphere, nitrogen, helium, argon gas or oxygen.
2. carry out the Trimethylmethane catalytic cracking reaction with the dual-function catalyst of gold-supported.
It is characterized in that described reaction raw materials is Trimethylmethane, the mixture of Trimethylmethane and normal butane, or the c of oil-gas field production 3, c 4cut can be also any c of Petrochemical Enterprises by-product 3, c 4cut; Can contain alkane and the alkene that is less than carbon four and is greater than carbon four in raw material, but the content of reactant Trimethylmethane preferably is not less than 50%.Reaction can and have under the condition of carrier gas at no carrier gas to be carried out.Described carrier gas is H 2, N 2, CO 2, CH 4, C 2h 6in one or two or more kinds mixture, carrier gas/hydrocarbon volume ratio optional 0～100.
(1) carry out the Trimethylmethane preparing olefin by catalytic cracking on fixed-bed reactor: catalyzer adopts conventional extruded moulding, temperature of reaction is 100 ~ 800 ℃, and preferably 150 ~ 600 ℃, reaction pressure is-0.07Mpa ~ 10MPa, preferably-0.05 ~ 3.0MPa, weight space velocity is 0.5 ~ 20h -1.
(2) carry out the Trimethylmethane preparing olefin by catalytic cracking on moving-burden bed reactor: catalyzer adopts conventional wear-resisting bead, and temperature of reaction is 100 ~ 800 ℃, and preferably 150 ~ 600 ℃, reaction pressure is 0.1 ~ 0.5MPa, and weight space velocity is 0.5 ~ 20h -1.
(3) carry out the Trimethylmethane preparing olefin by catalytic cracking on fluidized-bed reactor: catalyzer adopts the mist projection granulating moulding, and size range is the 20-120 micron.Temperature of reaction is 100 ~ 800 ℃, and preferably 150 ~ 600 ℃, reaction pressure is 0.1 ~ 0.3MPa, and agent hydrocarbon ratio is 0.5 ~ 5.
The invention has the beneficial effects as follows, by this method, can obtain metal-sour dual-function catalyst.The advantages such as prepared load gold catalyst has that the preparation method is simple, the granularity of gold particle high dispersive, gold grain is little.
Therefore this catalyzer, for the Trimethylmethane catalytic cracking reaction, has activity high, and temperature of reaction is low, the advantage that olefine selective is high.
Embodiment
Below by embodiment, the present invention will be further described, but the present invention is not subject to the restriction of these embodiment.
The comparative example 1:
Carry out the Trimethylmethane producing olefin hydrocarbon by catalytic pyrolysis on fixed-bed reactor.
(1). the method disclosed with reference to patent CN100364890C synthesizes the former powder of ZSM-5 zeolite, and the zeolite grain degree is less than 50nm.Then within 4 hours, obtain ZSM-5 zeolite 540 ℃ of lower roastings.
(2). the ammonium exchange is processed: baked zeolite is carried out to ion exchange treatment with ammonium salt solution at suitable temperature.Then, use deionized water wash, drier, roasting obtains h-type zeolite.Said ammonium salt is ammonium nitrate, and ammonium salt solution concentration is 0.6mol/L, and the liquid-solid volume ratio of ammonium salt solution and zeolite is 5:1, and exchange temperature is 30 ℃, and be 1 hour swap time, exchange times 2 times.110 ℃ of drying temperatures, 12 hours time of drying, maturing temperature is 540 ℃, roasting time is 6 hours.Na after exchange +content is not higher than 0.5%.
(3). sour reaming is processed: h-type zeolite is carried out at suitable acid concentration and temperature to sour reaming processing.Then extremely neutral with deionized water wash, drier, roasting obtains carrier.Said acid is HNO 3.Acid concentration is 0.6mol/L, the liquid-solid volume ratio 5:1 of acid solution and zeolite, and the sour reaming treatment time is 24 hours, treatment temp is 30 ℃.Drying temperature is 110 ℃, and be 12 hours time of drying, and maturing temperature selects 540 ℃, and roasting time is 3 hours, obtains the HZSM-5 zeolite catalyst.This catalyzer is carried out to NH 3tPD and infrared spectra acidity characterize.
(4). by pseudo-boehmite extruded moulding according to a conventional method for the HZSM-5 zeolite, the zeolite catalysis agent content is 80%, and the reaction time catalizer loadings is 2g, and raw material is Trimethylmethane, and isobutane purity is 99.5%, and the charging air speed is 1.0h -1, temperature of reaction is 520 ℃, reaction is carried out under no carrier gas and normal pressure.The reaction procatalyst is used nitrogen purging 30 minutes under temperature of reaction, is then reacted, and reacts sampling analysis after 4 hours.The Trimethylmethane transformation efficiency is 45%, and the selectivity of ethene+propylene+iso-butylene is: 31%, and the BTX aromatics selectivity: 22%, dry gas selectivity: 14%.
Embodiment 1:
The preparation method of 0.1%Au/HZSM-5:
(1). the method disclosed with reference to publication CN100364890C synthesizes the former powder of ZSM-5 molecular sieve.Then under 540 ° of C, roasting obtains ZSM-5 molecular sieve in 4 hours.
(2). the ammonium exchange is processed: baked molecular sieve is carried out to ion exchange treatment with ammonium salt solution at suitable temperature.Then, with deionized water wash, to neutral, drier, roasting obtains hydrogen type catalyst.Said ammonium salt is ammonium nitrate, and ammonium salt solution concentration is 0.6mol/L, and the liquid-solid volume ratio of catalyzer and ammonium salt solution is 5:1, and exchange temperature is 30 ° of C, and be 1 hour swap time, exchange times 2 times.110 ° of C of drying temperature, 12 hours time of drying, maturing temperature is 540 ° of C, roasting time is 6 hours.Na after exchange +content is not higher than 0.5%.
(3). sour reaming is processed: hydrogen type catalyst is carried out at suitable acid concentration and temperature to sour reaming processing.Then extremely neutral with deionized water wash, drier, roasting obtains catalyzer.Said acid is HNO 3.Acid concentration is 0.6mol/L, the liquid-solid volume ratio 5:1 of acid solution and catalyzer, and the sour reaming treatment time is 24 hours, treatment temp is 30 ℃.Drying temperature is 110 ° of C, and be 12 hours time of drying, and maturing temperature selects 540 ° of C, and roasting time is 3 hours.
In fact the hydrogen type catalyst obtained after the ammonium exchange just can directly be used as catalyzer.But sour reaming is to being conducive to improve the activity of catalyzer.
(4). with negative pressure deposition-precipitation method gold-supported: will carry out the negative pressure degasification purifying treatment under certain temperature through pretreated Hydrogen supersiliceous zeolite carrier.Then under fully stirring, first use golden precursor solution contact carrier, and then add precipitation agent to pass through negative pressure deposition sedimentation reaction load gold in mixture.Specifically: good molecular sieve 5g carries out the negative pressure degasification processing to get pre-treatment.The negative pressure degasification treatment temp is 80 ℃, and the degassed time is 5 hours, and range of negative pressure is-0.05MPa.Said golden precursor is HAuCl 4, said precipitation agent is analytical pure urea.Wherein, get HAuCl 4solution 1.26ml adds water to 10ml, HAuCl 4the suitable concentration of solution is 24.26mmol/L, and the Optimum of urea is 10g, and the volume ratio of golden precursor solution and molecular sieve carrier is 2:1, and pH is 8, and the deposition sedimentation temperature of reaction is 80 ℃, and churning time is 20 hours.After stirring stops standing 4 hours again.
(5). the solid substance to gold-supported carries out aftertreatment: comprise solid-liquid separation, with deionized water wash to without Cl -, and drying and the roasting of solid substance.Wherein, optional 100 ℃ of drying temperature, 12 hours time of drying, 400 ℃ of maturing temperatures, roasting time 4 hours, calcination atmosphere is air.Obtain the loading type Au/HZSM-5 zeolite [molecular sieve A-1 that particle diameter is less than 10nm.
Embodiment 2:
Repeat embodiment 1, but change the chlorauric acid solution consumption into 3.14ml, add water to 10ml, maturing temperature is 300 ℃.Obtain load type gold catalyst 0.3%Au/HZSM-5.Be designated as: A-2.
Embodiment 3:
Repeat embodiment 1, but vacuum tightness is changed into-0.05MPa, the chlorauric acid solution consumption changes 10.46ml into.Obtain load type gold catalyst 1.0%Au/HZSM-5.Be designated as: A-3.
Embodiment 4:
Repeat embodiment 1, but change the chlorauric acid solution consumption into 20.93.ml, maturing temperature is 500 ℃.Obtain load type gold catalyst 2.0%Au/HZSM-5.Be designated as: A-4.
Embodiment 5:
Repeat embodiment 1, but vacuum tightness is changed into-0.06MPa, the chlorauric acid solution consumption is 41.86ml, maturing temperature is 600 ℃.Obtain load type gold catalyst 3.0%Au/HZSM-5.Be designated as: A-5.
Embodiment 6:
Repeat embodiment 1, but change the 5th one-step baking equipment in embodiment 1 into the plasma body roasting, maturing temperature changes respectively 200 ℃, 300 ℃, 400 ℃, 500 ℃, 600 ℃ into, and calcination atmosphere is nitrogen.Obtain the load type gold catalyst after the differing temps roasting.The gold grain that granularity is less than 10nm is 90%.
Embodiment 7:
Repeat embodiment 1, but change respectively the pH value of golden precursor solution into 3,5,6,8,9 and 10.Obtain the load type gold catalyst of different pH values.The gold grain that is less than 10nm is 60～70%.
Embodiment 8:
Repeat embodiment 1, but change respectively the churning time of soluble solids into 1～24 hour, obtain 1.0Au/HZSM-5 and the 2.0%Au/HZSM-5 catalyzer of different churning time.Result shows: the stirring initial stage, and the hydroxy position that carrier surface can only provide small part can form surperficial gold complex, therefore less Radioactive colloidal gold can arrive nucleation site.Along with the prolongation of churning time, the pH value increases gradually, and the dispersion again that increasing surface hydroxyl position is colloid provides chance.Large golden aggregate splits, thereby generates the gold particle that a large amount of particle diameters is less.If continue time expand, considerable change will no longer occur in the particle diameter of gold particle.Optimum churning time is 18～20 hours.The gold grain that is less than 10nm is 60～70%.
Embodiment 9:
Repeat embodiment 1, but vacuum tightness is changed into respectively-0.01MPa ,-0.03MPa ,-0.05MPa ,-0.07MPa ,-1.0MPa.Obtain the load type gold catalyst of different vacuum tightnesss.The gold grain that is less than 10nm is 60～70%.
Embodiment 10:
Repeat embodiment 1, but carrier is changed to the HZSM-8 molecular sieve, the method that the ZSM-8 molecular sieve discloses with reference to publication CN101703944A (2010) synthesizes the ZSM-8 molecular screen primary powder.Then under 540 ° of C, roasting obtains the ZSM-8 molecular sieve in 4 hours.The chlorauric acid solution consumption is 1.26ml.Obtain load type gold catalyst 0.1%Au/HZSM-8.The gold grain that is less than 10nm is 90%.Be designated as: A-6.
Embodiment 11:
Repeat embodiment 1, but carrier is changed to the HZSM-11 molecular sieve, the method that the ZSM-11 molecular sieve discloses with reference to publication CN1367758 (2002) synthesizes the ZSM-11 molecular screen primary powder.Then under 540 ° of C, roasting obtains the ZSM-11 molecular sieve in 4 hours.The chlorauric acid solution consumption is 3.14ml, and maturing temperature is 400 ℃.Obtain load type gold catalyst 0.3%Au/HZSM-11.The gold grain that is less than 10nm is 80%.Be designated as: A-7.
Embodiment 12:
Repeat embodiment 1, but carrier is changed to the HZSM-12 molecular sieve, the method that the ZSM-12 molecular sieve discloses with reference to publication CN1774398 (2006) synthesizes the ZSM-12 molecular screen primary powder.Then under 540 ° of C, roasting obtains the ZSM-12 molecular sieve in 4 hours.The chlorauric acid solution consumption is 3.14ml, and maturing temperature is 400 ℃.Obtain load type gold catalyst 0.3%Au/HZSM-12.The gold grain that is less than 10nm is 90%.Be designated as: A-8.
Embodiment 13:
Repeat embodiment 1, but carrier is changed to the MCM-22 molecular sieve, the method that the MCM-22 molecular sieve discloses with reference to publication CN1328960A (2002) synthesizes the MCM-22 molecular screen primary powder.Then under 540 ° of C, roasting obtains the MCM-22 molecular sieve in 4 hours.Vacuum tightness is-0.05MPa, and the chlorauric acid solution consumption is 10.46ml, and maturing temperature is 400 ℃.Obtain load type gold catalyst 1.0%Au/MCM-22.The gold grain that is less than 10nm is 94%.Be designated as: A-9.
Embodiment 14:
Repeat embodiment 1, but carrier is changed to the MCM-49 molecular sieve, the method that the MCM-49 molecular sieve discloses with reference to publication CN101468800 (2009) synthesizes the MCM-49 molecular screen primary powder.Then under 540 ° of C, roasting obtains the MCM-49 molecular sieve in 4 hours.Vacuum tightness is-0.06MPa, and the chlorauric acid solution consumption is 20.93ml, and maturing temperature is 500 ℃.Obtain load type gold catalyst 2.0%Au/MCM-49.The gold grain that is less than 10nm is 92%.Be designated as: A-10.
Embodiment 15:
Repeat embodiment 1, but carrier is changed to the MCM-56 molecular sieve, the method that the MCM-56 molecular sieve discloses with reference to publication CN101007637A (2007) synthesizes the MCM-56 molecular screen primary powder.Then under 540 ° of C, roasting obtains the MCM-56 molecular sieve in 4 hours.Vacuum tightness is-0.05MPa, and the chlorauric acid solution consumption is 41.86ml, and maturing temperature is 500 ℃.Obtain load type gold catalyst 3.0%Au/MCM-56.The gold grain that is less than 10nm is 91%.Be designated as: A-11.
Embodiment 16:
Repeat embodiment 1, but carrier is changed to the ITQ-2 molecular sieve, the method that the ITQ-2 molecular sieve discloses with reference to publication CN101973560A (2011) synthesizes the ITQ-2 molecular screen primary powder.Then under 540 ° of C, roasting obtains the ITQ-2 molecular sieve in 4 hours.Vacuum tightness is-0.05MPa, and the chlorauric acid solution consumption is 15.70ml, and maturing temperature is 400 ℃.Obtain load type gold catalyst 1.5%Au/ITQ-2.The gold grain that is less than 10nm is 90%.Be designated as: A-12.
Embodiment 17:
Repeat embodiment 1, but carrier is changed to the H beta-molecular sieve, the method that the H beta-molecular sieve discloses with reference to publication CN1086792A (1994) synthesizes the former powder of H beta-molecular sieve.Then under 540 ° of C, roasting obtains the H beta-molecular sieve in 4 hours.Vacuum tightness is-0.05MPa, and the chlorauric acid solution consumption is 10.46ml, and maturing temperature is 400 ℃.Obtain load type gold catalyst 1.0%Au/H β.The gold grain that is less than 10nm is 80%.Be designated as: A-13.
Embodiment 18:
Repeat embodiment 1, but carrier is changed to the S-1 molecular sieve, vacuum tightness is-0.045MPa, and the chlorauric acid solution consumption is 6.28ml, and maturing temperature is 400 ℃.Obtain load type gold catalyst 0.5%Au/S-1.The gold grain that is less than 10nm is 90%.Be designated as: A-14.
Embodiment 19:
Repeat embodiment 1, but carrier is changed to the TS-1 molecular sieve, the method that the TS-1 molecular sieve discloses with reference to publication CN100457622A (2001) synthesizes the TS-1 molecular screen primary powder.Then under 540 ° of C, roasting obtains the TS-1 molecular sieve in 4 hours.Vacuum tightness is-0.04MPa, and the chlorauric acid solution consumption is 6.28ml, and maturing temperature is 400 ℃.Obtain load type gold catalyst 0.5%Au/TS-1.The gold grain that is less than 10nm is 90%.Be designated as: A-15.
Embodiment 20:
Repeat embodiment 1, but carrier is changed to the ZSM-22 molecular sieve, the method that the ZSM-22 molecular sieve discloses with reference to publication US5783168A (1998) synthesizes the ZSM-22 molecular screen primary powder.Then under 540 ° of C, roasting obtains the ZSM-22 molecular sieve in 4 hours.Vacuum tightness is-0.04MPa, and the chlorauric acid solution consumption is 6.28ml, and maturing temperature is 400 ℃.Obtain load type gold catalyst 0.5%Au/TS-1.The gold grain that is less than 10nm is 75%.Be designated as: A-16.
Embodiment 21:
Repeat embodiment 1, but change the precipitation agent consumption into 10g, vacuum tightness is-0.04MPa that maturing temperature is 400 ℃.Obtain load type gold catalyst 2.0%Au/HZSM-5.Be designated as: A-17.
Embodiment 22:
Repeat embodiment 1, change the precipitation agent consumption into 3g, vacuum tightness is-0.04MPa that maturing temperature is 400 ℃.Obtain the 2.0%Au/HZSM-5 catalyzer.Be designated as: A-18.
Embodiment 23:
The preparation method of 0.1%Au-3.0%Zn/HZSM-5:
(1). the method disclosed with reference to publication CN100364890C synthesizes the former powder of ZSM-5 molecular sieve.Then under 540 ° of C, roasting obtains ZSM-5 molecular sieve in 4 hours.
(2). the ammonium exchange is processed: baked molecular sieve is carried out to ion exchange treatment with ammonium salt solution at suitable temperature.Then, with deionized water wash, to neutral, drier, roasting obtains hydrogen type catalyst.Said ammonium salt is ammonium nitrate, and ammonium salt solution concentration is 0.6mol/L, and the liquid-solid volume ratio of catalyzer and ammonium salt solution is 5:1, and exchange temperature is 30 ° of C, and be 1 hour swap time, exchange times 2 times.110 ° of C of drying temperature, 12 hours time of drying, maturing temperature is 540 ° of C, roasting time is 6 hours.Na after exchange +content is not higher than 0.5%.
(3). sour reaming is processed: hydrogen type catalyst is carried out at suitable acid concentration and temperature to sour reaming processing.Then extremely neutral with deionized water wash, drier, roasting obtains catalyzer.Said acid is HNO 3.Acid concentration is 0.6mol/L, the liquid-solid volume ratio 5:1 of acid solution and catalyzer, and the sour reaming treatment time is 24 hours, treatment temp is 30 ℃.Drying temperature is 110 ° of C, and be 12 hours time of drying, and maturing temperature selects 540 ° of C, and roasting time is 3 hours.
In fact the hydrogen type catalyst obtained after the ammonium exchange just can directly be used as catalyzer.But sour reaming is to being conducive to improve the activity of catalyzer.
(4) with negative pressure deposition-precipitation method gold-supported: will carry out the negative pressure degasification purifying treatment under certain temperature through pretreated Hydrogen supersiliceous zeolite carrier.Then under fully stirring, first use golden precursor solution contact carrier, and then add precipitation agent to pass through negative pressure deposition sedimentation reaction load gold in mixture.Specifically: good molecular sieve 5g carries out the negative pressure degasification processing to get pre-treatment.The negative pressure degasification treatment temp is 80 ℃, and the degassed time is 5 hours, and range of negative pressure is-0.05MPa.Said golden precursor is HAuCl 4, said precipitation agent is analytical pure urea.Wherein, get HAuCl 4solution 1.26ml adds water to 10ml, HAuCl 4the suitable concentration of solution is 24.26mmol/L, and the Optimum of urea is 10g, and the volume ratio of golden precursor solution and molecular sieve carrier is 2:1, and pH is 8, and the deposition sedimentation temperature of reaction is 80 ℃, and churning time is 20 hours.After stopping, stirring floods again 4 hours.
(5). with negative pressure impregnation the second metal: the load type gold catalyst that will prepare through the negative pressure deposition-precipitation method carries out the negative pressure degasification purifying treatment at a certain temperature.Then under fully stirring, by negative pressure impregnation method load the second metal.The negative pressure degasification treatment temp is 80 ℃, and the degassed time is 4 hours, and range of negative pressure is-0.45MPa.Although higher vacuum tightness is favourable to purifying, can increase the catalyzer cost of manufacture.Said the second metal is Zn.Zinc salt is zinc nitrate, and the zinc nitrate suitable concentration is 10mol/L, and the volume ratio of metallic precursor solution and molecular sieve carrier is 3:1, optional 80 ℃ of dipping temperature, optional 4 hours of churning time.
(6). the bimetallic solid substance of load regulation is carried out to aftertreatment: comprise drying and the roasting of solid-liquid separation, use deionized water wash and solid substance.Wherein, optional 100 ℃ of drying temperature, 12 hours time of drying, 400 ℃ of maturing temperatures, roasting time 4 hours, calcination atmosphere is air.Obtain the loading type Au-Zn/HZSM-5 zeolite [molecular sieve A-19 that the goldc grains footpath is less than 10nm.
Embodiment 24:
Repeat embodiment 23, but change successively the second activity component metal in Fe, Mo, Ni, Ga, Co, Pt, Pd, Ag and Cu any one.Maturing temperature is 300 ℃.Obtaining load type gold catalyst Au-M/HZSM-5(M is the second activity component metal).The gold grain that is less than 10nm is 60～90%.Be designated as: A-20 ~ A-28.
Embodiment 25:
Repeat embodiment 23, but change the chlorauric acid solution consumption into 20.93ml, be diluted with water to 25ml, obtain 1.96%Au-2.94%Zn/HZSM-5, be labeled as A-29.
Embodiment 26:
Repeat embodiment 23, but change successively the nitric acid zinc concentration into 0.13mol/L, 0.26mol/L, 1.54mol/L, 2.31mol/L, obtain successively 0.1%Au-0.5%Zn/HZSM-5,0.1%Au-1.0%Zn/HZSM-5,0.1%Au-6.0%Zn/HZSM-5,0.1%Au-9.0%Zn/HZSM-5 is labeled as A-30 ~ A33.
Embodiment 27:
Repeat embodiment 23, but change successively the second active metal component into Fe, Co, Ni, Ga, Cu, the second metal is introduced charge capacity with nitrate and is changed 1.0% into, obtain in proper order load type gold catalyst 1.0%Au-1.0%Fe/HZSM-5,1.0%Au-1.0%Co/HZSM-5,1.0%Au-1.0%Ni/HZSM-5,1.0%Au-1.0%Ga/HZSM-5,1.0%Au-1.0%Cu/HZSM-5(M is the second activity component metal).
Embodiment 28:
Repeat embodiment 23, but change the 5th step pressure in embodiment 23 into normal pressure, the second activity component metal changes any one in Fe, Mo, Ni, Ga, Co, Pt, Pd, Ag and Cu successively into.Maturing temperature is 540 ℃.Obtaining load type gold catalyst Au-M/HZSM-5(M is the second activity component metal).The gold grain that is less than 10nm is 60～70%.
Embodiment 29:
Repeat embodiment 23, but change the roasting of the 6th step catalyzer in embodiment 23 under nitrogen atmosphere plasma body roasting, maturing temperature is 300～600 ℃, and the second activity component metal changes any one in Fe, Mo, Ni, Ga, Co, Pt, Pd, Ag and Cu successively into.Obtaining load type gold catalyst Au-M/HZSM-5(M is the second activity component metal).The gold grain that is less than 10nm is 60～90%.
Embodiment 30:
Repeat embodiment 23, but the calcination atmosphere of the 6th step catalyzer in embodiment 23 is changed successively into to any one of helium, argon gas, air, oxygen atmosphere, roasting apparatus changes the plasma body roasting into, maturing temperature is 300～600 ℃, and the second activity component metal changes any one in Fe, Mo, Ni, Ga, Co, Pt, Pd, Ag and Cu successively into.Obtaining load type gold catalyst Au-M/HZSM-5(M is the second activity component metal).The gold grain that is less than 10nm is 60～90%.
Embodiment 31:
Repeat embodiment 1, but the large grain ZSM-5 that synthetic grain fineness number is 5 μ m as follows, and the consumption of change urea precipitation agent, make the pH value be respectively 3,5,6,8,9 and 10.The method of synthetic ZSM-5 zeolite is: first take a certain amount of industrial aluminum sulphate and use deionized water dissolving, then adding wherein sulfuric acid, after stirring, as A solution; Take again a certain amount of water glass and be diluted with water to B solution.Then, under vigorous stirring, A solution slowly is added drop-wise in B solution, (the crystal seed synthetic method is with reference to patent: ZL200510200328.9) to add a certain amount of crystal seed after reinforced, continue to stir 2h, obtain even gel, make mole consisting of of gel: SiO 2/ Al 2o 3=50; Na 2o/SiO 2=0.078; H 2o/SiO 2=900; Amount of seed is 5% (SiO in synthetic system 2mass percent).By the gained gel crystallization in the stainless steel crystallizing kettle of packing into.Crystallization temperature is 170 ℃, and crystallization time is 18h.After crystallization, suction method is removed mother liquor and filter cake is washed till to neutrality, under 110 ℃, dries, and obtains the former powder of Na type ZSM-5 zeolite.Obtain the 2.0%Au/HZSM-5 load type gold catalyst.Be designated as: A-39.
Embodiment 32:
Repeat embodiment 1, but the strip ZSM-5 zeolite that synthetic grain fineness number is 10 μ m with the following method changes the precipitation agent consumption simultaneously, making the pH value is 5.The method of synthetic zeolite is: take a certain amount of industrial aluminum sulphate and use deionized water dissolving, then adding wherein sulfuric acid, after stirring, as A solution; Take again a certain amount of water glass and be diluted with water to B solution.Then, under vigorous stirring, A solution and the dehydrated alcohol that measures slowly are added drop-wise in B solution successively, continue to stir 2h after reinforced, obtain mole consisting of of even gel: SiO 2/ Al 2o 3=60; Na 2o/SiO 2=0.1; Ethanol/SiO 2=1.5; H 2o/SiO 2=900; Amount of seed is 5% (SiO in synthetic system 2mass percent).By the gained gel crystallization in the stainless steel crystallizing kettle of packing into.Crystallization temperature is 170 ℃, and crystallization time is 20h.After crystallization, with suction method, remove mother liquor and filter cake is washed till to neutrality, dry under 110 ℃, obtain Na type ZSM-5 zeolite molecular screen primary powder.Obtain the 2.0%Au/HZSM-5 load type gold catalyst.Be designated as: A-40.
Embodiment 33:
Carry out the Trimethylmethane producing olefin hydrocarbon by catalytic pyrolysis on fixed-bed reactor.
By the A-1 catalyst sample of above-mentioned preparation, with pseudo-boehmite extruded moulding according to a conventional method, zeolite content is 80%, and the reaction time catalizer loadings is 2g, and raw material is that Trimethylmethane (purity is 99.5%) charging air speed is 1.05h -1, temperature of reaction is 530 ℃, and reaction is carried out under normal pressure no carrier gas condition, and the reaction procatalyst is used nitrogen purging 30 minutes under temperature of reaction, is then reacted.React sampling analysis after 4 hours, the Trimethylmethane transformation efficiency is 73%, and the selectivity of ethene+propylene+iso-butylene is: 26%, and the BTX aromatics selectivity: 36%, dry gas selectivity: 20%.
Embodiment 34:
Repeat embodiment 33, but change catalyzer into A-3, temperature of reaction changes 530 ℃ into, and the Trimethylmethane transformation efficiency is 65%, and the selectivity of ethene+propylene+iso-butylene is: 30%, and the BTX aromatics selectivity: 12%, dry gas selectivity: 12%
Embodiment 35:
Repeat embodiment 33, but change catalyzer into A-4, temperature of reaction changes 530 ℃ into, and the Trimethylmethane transformation efficiency is 80%, and the selectivity of ethene+propylene+iso-butylene is: 30%, and the BTX aromatics selectivity: 36%, dry gas selectivity: 11%.
Embodiment 36:
Repeat embodiment 33, but change catalyzer into A-6, temperature of reaction changes 550 ℃ into, and reaction pressure changes 1.5MPa into, and the charging air speed changes 10h into -1, the Trimethylmethane transformation efficiency is 76%, the selectivity of ethene+propylene+iso-butylene is: and 18%, the BTX aromatics selectivity: 42%, dry gas selectivity: 20%.
Embodiment 37:
Repeat embodiment 33, but change catalyzer into A-7, temperature of reaction changes 500 ℃ into, and reaction pressure changes 3.0MPa into, and the charging air speed changes 20h into -1, the Trimethylmethane transformation efficiency is 38%, the selectivity of ethene+propylene+iso-butylene is: and 20%, the BTX aromatics selectivity: 37%, dry gas selectivity: 13%.
Embodiment 38:
Repeat embodiment 33, but change catalyzer into A-8, temperature of reaction changes 530 ℃ into, reaction is carried out facing in the hydrogen situation, and hydrogen/hydrocarbon volume ratio is 10/1, and the Trimethylmethane transformation efficiency is 45%, the selectivity of ethene+propylene+iso-butylene is: 31%, and the BTX aromatics selectivity: 22%, dry gas selectivity: 14%.
Embodiment 39:
Repeat embodiment 33, but change catalyzer into A-9, reaction pressure changes 1.6MPa into, under the condition that reaction is carrier gas at nitrogen, carry out, the volume ratio of nitrogen/hydrocarbon is 50/1, and the Trimethylmethane transformation efficiency is 61%, and the selectivity of ethene+propylene+iso-butylene is: 38%, the BTX aromatics selectivity: 19%, dry gas selectivity: 16%.
Embodiment 40:
Repeat embodiment 33, but by catalyzer change into A-11, A-12, A-13, A-14, A-15, A-18 the Trimethylmethane transformation efficiency be followed successively by 54%, 56%, 60%, 62%, 68%, 71%, the selectivity of ethene+propylene+iso-butylene is followed successively by: 22%, 32%, 29%, 38%, 24%, 36%, the BTX aromatics selectivity is followed successively by: 31%, 26%, 28%, 26%, 33%, 29%, the dry gas selectivity is followed successively by: 14%, 10%, 15%, 19%, 14%, 11%.
Embodiment 41:
Repeat embodiment 33, but change successively catalyzer into A-19, A-20, the Trimethylmethane transformation efficiency is followed successively by 81%, 90%, the selectivity of ethene+propylene+iso-butylene is followed successively by: 32%, 39%, and the BTX aromatics selectivity is followed successively by: 36%, 31%, the dry gas selectivity is followed successively by: 14%, 16%.
Embodiment 42:
Repeat embodiment 33, but change successively catalyzer into A-21, A-22, A-23, A-24, A-25, A-26, A-27, A-28, the Trimethylmethane transformation efficiency is all between 80-90% for A-29, and the selectivity of ethene+propylene+iso-butylene is all between 30%-40%, the BTX aromatics selectivity is all between 25%-40%, and the dry gas selectivity is all between 10%-25%.
Embodiment 43:
Repeat embodiment 33, but change catalyzer into A-23, temperature of reaction changes 530 ℃ into, change into-0.07MPa of reaction pressure, the Trimethylmethane transformation efficiency is 81%, the selectivity of ethene+propylene+iso-butylene is: 65%, the BTX aromatics selectivity: 10%, dry gas selectivity: 10%.
Embodiment 44:
Repeat embodiment 33, but change catalyzer into A-24, temperature of reaction changes 550 ℃ into, change into-0.04MPa of reaction pressure, the Trimethylmethane transformation efficiency is 88%, the selectivity of ethene+propylene+iso-butylene is: 45%, the BTX aromatics selectivity: 25%, dry gas selectivity: 14%.
Embodiment 45:
Repeat embodiment 33, but change catalyzer into A-20, temperature of reaction changes 530 ℃ into, and reaction pressure changes 1.6MPa into, reaction is carried out under hydro condition, hydrogen/hydrocarbon volume ratio is 100/1, and reaction raw materials changes mixed butanes into, and its normal butane and Trimethylmethane proportioning are 85%:15%, the Trimethylmethane transformation efficiency is 86%, the selectivity of ethene+propylene+iso-butylene is: 30%, and the BTX aromatics selectivity: 37%, dry gas selectivity: 17%.
Embodiment 46:
Repeat embodiment 33, but change catalyzer into A-23, change reaction raw materials into rich butane liquefied gas, wherein Trimethylmethane content is 55%, normal butane content 1.5%, butene content 35%, be less than butane and the alkene sum is 3.5%, and being greater than butane and alkene sum is 5%, the Trimethylmethane transformation efficiency is 79%, the selectivity of ethene+propylene+iso-butylene is: 48%, and the BTX aromatics selectivity: 21%, dry gas selectivity: 13%.
Embodiment 47:
Repeat embodiment 33, but change catalyzer into A-25, the reaction carrier gas is changed into to the mixture of hydrogen and methane, ethane, wherein the content of hydrogen is 60%, the volume ratio of total carrier gas/hydrocarbon is 100/1, and the Trimethylmethane transformation efficiency is 71%, and the selectivity of ethene+propylene+iso-butylene is: 52%, the BTX aromatics selectivity: 16%, dry gas selectivity: 9%.
Embodiment 48:
Repeat embodiment 33, but change catalyzer into A-26, no carrier gas, change into-0.05MPa of reaction pressure, the Trimethylmethane transformation efficiency is 80%, the selectivity of ethene+propylene+iso-butylene is: 58%, the BTX aromatics selectivity: 18%, dry gas selectivity: 12%.
Embodiment 49:
Carry out the Trimethylmethane preparing olefin by catalytic cracking on moving-burden bed reactor.
The A-20 catalyst sample of above-mentioned preparation is made to wear-resisting bead, the wear-resisting pellet catalyst of 1000 gram is packed in small-sized movable bed testing installation, raw material is rich butane liquefied gas, wherein Trimethylmethane content is 55%, normal butane content 1.5%, butene content 35%, be less than butane and the alkene sum is 3.5%, and being greater than butane and alkene sum is 5%; Temperature of reaction is 530 ℃, and reaction pressure is 0.5MPa, and the charging air speed is 3h -1, hydrogen is carrier gas, hydrogen/hydrocarbon volume ratio is 50/1.The Trimethylmethane transformation efficiency is 86%, and the selectivity of ethene+propylene+iso-butylene is: 47%, and the BTX aromatics selectivity: 21%, dry gas selectivity: 15%.
Embodiment 50:
Repeat embodiment 49, but be 480 ℃ by temperature of reaction, the charging air speed changes 0.5h into -1, the Trimethylmethane transformation efficiency is 42%, the selectivity of ethene+propylene+iso-butylene is: and 44%, the BTX aromatics selectivity: 9%, dry gas selectivity: 8%.
Embodiment 51:
Repeat embodiment 49, but change reaction raw materials into rich butane mixed c 4, wherein Trimethylmethane content is 70%, normal butane content 1.0%, butene content 25%, being less than butane and alkene sum is 1.5%, being greater than butane and alkene sum is 2.5%, and the Trimethylmethane transformation efficiency is 38%, and the selectivity of ethene+propylene+iso-butylene is: 50%, the BTX aromatics selectivity: 10%, dry gas selectivity: 9%.
Embodiment 52:
Carry out the Trimethylmethane preparing olefin by catalytic cracking on fluidized-bed reactor.
The A-21 catalyzer of above-mentioned preparation is made to the powder of 20-120 micron by the conventional mist projection granulating method of forming.1000 gram catalyzer are packed in the small-sized fluidized bed testing apparatus, and raw material is mixed c 4, and wherein Trimethylmethane content is 55%, normal butane content 1.5%, and butene content 35%, be less than butane and the alkene sum is 3.5%, and being greater than butane and alkene sum is 5%; Temperature of reaction is 500 ℃, and reaction pressure is 0.2MPa, and agent/hydrocarbon ratio is 5; The mixture of hydrogen and methane, ethane is carrier gas, and wherein the content of hydrogen is 60%, and the volume ratio of total carrier gas/hydrocarbon is 100/1.The Trimethylmethane transformation efficiency is 84%, and the selectivity of ethene+propylene+iso-butylene is: 53%, and the BTX aromatics selectivity: 16%, dry gas selectivity: 15%.
Embodiment 53:
Repeat embodiment 52, but change raw material into rich butane mixed c 4, wherein Trimethylmethane content is 70%, normal butane content 1.0%, butene content 25%, being less than butane and alkene sum is 1.5%, being greater than butane and alkene sum is 2.5%, and the Trimethylmethane transformation efficiency is 79%, and the selectivity of ethene+propylene+iso-butylene is: 56%, the BTX aromatics selectivity: 20%, dry gas selectivity: 10%.
Embodiment 54:
Repeat embodiment 52, but be 400 ℃ by temperature of reaction, the Trimethylmethane transformation efficiency is 41%, and the selectivity of ethene+propylene+iso-butylene is: 55%, and the BTX aromatics selectivity: 8%, dry gas selectivity: 8%.
Embodiment 55:
Repeat embodiment 52, but be 1 by agent/hydrocarbon ratio, the Trimethylmethane transformation efficiency is 86%, and the selectivity of ethene+propylene+iso-butylene is: 35%, and the BTX aromatics selectivity: 32%, dry gas selectivity: 15%.

Claims (7)

1. a modified molecular sieve catalyst, for the method for Trimethylmethane catalytic pyrolysis, is characterized in that comprising the steps:
A. the supersiliceous zeolite carrier is carried out to pre-treatment
(1) the supersiliceous zeolite carrier is carried out to calcination process; Maturing temperature selects 400～600 ℃, and roasting time is 3～8 hours; The silica alumina ratio of supersiliceous zeolite is greater than 10, and the grain fineness number of zeolite is at 5nm ~ 30 μ m;
(2) the ammonium exchange is processed: baked zeolite is carried out to ion exchange treatment with 0.05～1.0mol/L ammonium nitrate, ammonium chloride or sal volatile under 20 ~ 80 ℃, and the liquid-solid volume ratio of ammonium salt solution and zeolite is 3:1 ~ 10:1; Be 0.2～100 hour swap time, and exchange times 1 ~ 5 time is controlled Na +content is less than 1.0%; Then use deionized water wash, then carry out drying and calcination process obtains h-type zeolite; 80 ~ 200 ℃ of drying temperatures, 1 ~ 100 hour time of drying; 400 ~ 600 ℃ of maturing temperatures, roasting time 3 ~ 8 hours;
(3) sour reaming is processed: with HCl, HNO 3, H 2sO 4or the solution of citric acid carries out sour reaming processing to h-type zeolite; Then extremely neutral with deionized water wash, drier, roasting obtains carrier; Acid concentration is 0.05 ~ 6mol/L, the liquid-solid volume ratio 3:1 of acid solution and zeolite ~ 10:1, and the sour reaming treatment time is 1 ~ 5 hour, treatment temp is 20 ~ 80 ℃; Drying temperature is 50 ~ 200 ℃, and be 3 ~ 20 hours time of drying; Maturing temperature is 300 ~ 600 ℃, and roasting time is 1 ~ 4 hour;
B. under condition of negative pressure, adopt deposition-precipitation method to prepare load gold catalyst
(1) with negative pressure deposition-precipitation method gold-supported: will carry out the negative pressure degasification purifying treatment through pretreated h-type zeolite carrier, treatment temp is 20～90 ℃, and the degassed time is 0.5～12 hour, range of negative pressure is-0.01～-0.1MPa; Then under agitation keep temperature and negative pressure state, first use golden precursor solution contact carrier, and then add precipitation agent to pass through negative pressure deposition sedimentation reaction load gold in mixture, the reaction times is 5～100 hours;
(2) throw out of gold-supported carried out to aftertreatment: comprise solid-liquid separation, with deionized water wash to without Cl -, the drying of solid substance and roasting; 80～200 ℃ of drying temperatures, 0.5～100 hour time of drying; 300 ~ 700 ℃ of maturing temperatures; Roasting time 3 ~ 20 hours; Retort furnace or plasma body roasting are selected in roasting; Calcination atmosphere is nitrogen, helium, argon gas, air or oxygen;
C. on reactor, the Trimethylmethane catalytic pyrolysis generates alkene
(1) carry out the Trimethylmethane preparing olefin by catalytic cracking on fixed-bed reactor: catalyzer adopts conventional extruded moulding, and temperature of reaction is 150 ~ 600 ℃, and reaction pressure is-0.05 ~ 3.0MPa, and weight space velocity is 0.5 ~ 20h -1;
(2) carry out the Trimethylmethane preparing olefin by catalytic cracking on moving-burden bed reactor: catalyzer adopts conventional wear-resisting bead, and temperature of reaction is 150 ~ 600 ℃, and reaction pressure is 0.1 ~ 0.5MPa, and weight space velocity is 0.5 ~ 20h -1;
(3) carry out the Trimethylmethane preparing olefin by catalytic cracking on fluidized-bed reactor: catalyzer adopts the mist projection granulating moulding, and size range is the 20-120 micron; Temperature of reaction is 150 ~ 600 ℃, and reaction pressure is 0.1 ~ 0.3MPa, and agent hydrocarbon ratio is 0.5 ~ 5.
2. method according to claim 1, is characterized in that, said supersiliceous zeolite refers to ZSM-5, ZSM-8, ZSM-11, MCM-22, MCM-49, MCM-56, ITQ-2, ZSM-12, beta-zeolite, mordenite, TS-1 or pure silicon zeolite.
3. method according to claim 1, is characterized in that described golden precursor is HAuC 14, wherein, HAuCl 4concentration be 5～50mmol/L, the volume ratio of golden precursor solution and carrier is 1:1～10:1, pH is 4～9.
4. method according to claim 1, is characterized in that described precipitation agent is urea, by precipitation agent regulator solution pH value, is 4～9.
5. according to claim 1,2,3 or 4 described methods, it is characterized in that flooding the second metal by the employing pickling process on the catalyzer of gold-supported: the negative pressure degasification treatment temp is 20～90 ℃, the degassed time is 0.5～2 hour, range of negative pressure is-0.01～-0.1MPa; Then under agitation keep the temperature and pressure state to flood the second metal, the second metal is Zn, Fe, Mo, Ni, Ga, Co, Pt, Pd, Ag or Cu; The second metal is introduced with nitrate or hydrochloride, and concentration is 0.1～2mol/L, and the volume ratio of golden precursor solution and carrier is 1:1～10:1, dipping time 0.5-24 hour; The bimetallic solid substance of load regulation is carried out to aftertreatment: comprise solid-liquid separation, the drying of solid substance and roasting; Drying temperature is 50 ~ 200 ℃, and be 3 ~ 20 hours time of drying; Maturing temperature selects 300 ~ 700 ℃; Roasting time is 3 ~ 20 hours; Roasting is retort furnace or plasma body roasting; Calcination atmosphere is nitrogen, helium, argon gas, air or oxygen.
6. method according to claim 1, is characterized in that described reaction raw materials is Trimethylmethane, the mixture of Trimethylmethane and normal butane, the C 4 fraction after oil-gas field is produced, any C 4 fraction of Petrochemical Enterprises by-product; Contain the alkane and the alkene that are less than carbon four and are greater than carbon four in raw material, but the content of reactant Trimethylmethane is not less than 50%.
7. method according to claim 5, is characterized in that described reaction is to carry out under the condition existed in carrier gas, and described carrier gas is H 2, N 2, CO 2, CH 4, C 2h 6in one or two or more kinds mixture, carrier gas/hydrocarbon volume ratio is 0～100.
CN2013100505995A 2013-02-07 2013-02-07 Method of using modified molecular sieve catalyst in isobutane catalytic cracking Pending CN103130604A (en)

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CN111389457A (en) * 2020-04-22 2020-07-10 陕西延长石油（集团）有限责任公司 Catalyst and method for preparing methacrylic acid and propylene oxide by co-oxidation of isobutane and propylene
CN112221490A (en) * 2019-06-30 2021-01-15 中国石油化工股份有限公司 Isobutane dehydrogenation catalyst with modified hexagonal mesoporous material containing Mg and/or Ti components as carrier and preparation method and application thereof
CN113333016A (en) * 2021-05-21 2021-09-03 山东省科学院能源研究所 Nano-scale KL molecular sieve loaded metal catalyst, preparation method and application
CN113441171A (en) * 2021-05-12 2021-09-28 中新国际联合研究院 Carrier modified silver-based ethylene remover and preparation method and application thereof
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CN105647772A (en) * 2014-12-26 2016-06-08 淮阴工学院 Aging accelerating method on basis of baijiu aging accelerating agents
CN108349831A (en) * 2015-10-21 2018-07-31 艾克瑟路斯股份有限公司 The method that reaction by methanol and/or DME or the reaction by methanol and/or DME and butane prepare alkene or alkylates
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CN110614095A (en) * 2018-06-20 2019-12-27 中国石油化工股份有限公司 Isobutane dehydrogenation catalyst with spherical double-mesoporous sepiolite composite material as carrier and preparation method and application thereof
CN112221490A (en) * 2019-06-30 2021-01-15 中国石油化工股份有限公司 Isobutane dehydrogenation catalyst with modified hexagonal mesoporous material containing Mg and/or Ti components as carrier and preparation method and application thereof
CN111389457A (en) * 2020-04-22 2020-07-10 陕西延长石油（集团）有限责任公司 Catalyst and method for preparing methacrylic acid and propylene oxide by co-oxidation of isobutane and propylene
CN111389457B (en) * 2020-04-22 2022-08-30 陕西延长石油（集团）有限责任公司 Catalyst and method for preparing methacrylic acid and propylene oxide by co-oxidation of isobutane and propylene
CN113441171A (en) * 2021-05-12 2021-09-28 中新国际联合研究院 Carrier modified silver-based ethylene remover and preparation method and application thereof
CN113333016A (en) * 2021-05-21 2021-09-03 山东省科学院能源研究所 Nano-scale KL molecular sieve loaded metal catalyst, preparation method and application
CN116474679A (en) * 2023-04-27 2023-07-25 宁波昊德化学工业股份有限公司 Method and equipment for producing isobutene

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