CN103143386A - Method for converting n-paraffins into isoparaffins through using gold supported molecular sieve catalyst - Google Patents

Abstract

A method for converting n-paraffins into isoparaffins through using a gold supported molecular sieve catalyst belongs to the technical field of catalysts. A molecular sieve is subjected to full negative-pressure degassing purifying treatment, and a gold precursor is loaded on the molecular sieve carrier through adopting a negative-pressure deposition-precipitation method to obtain the uniform-dispersion small-granule supported nano-gold catalyst. The molecular sieve is a high-silicon zeolite molecular sieve, and the preparation of the gold supported catalyst through the deposition-precipitation method under a negative pressure is in favor of cleaning the internal and external surfaces and the tunnels of the molecular sieve, so Au can easily enter the tunnels of the molecular sieve to reach high dispersion. The method provided by the invention allows n-paraffins to be dehydrogenated under the metal and carrier difunctional action to generate olefins, olefins obtain protons from acid sites to form carbonium ions, and the carbonium ions undergo skeletal isomerization and hydrogenation desorption to generate isoparaffins.

Description

A kind of molecular sieve catalyst with gold-supported transforms the method that n-alkane is isoparaffin

Technical field

The invention belongs to catalyst technical field, relate to a kind of molecular sieve catalyst with gold-supported and transform the method that n-alkane is isoparaffin.

Background technology

Positive structure hydrocarbon isomerization is one of important reaction of petrochemical industry, and isohydrocarbon has purposes widely.For example, normal butane is converted into to iso-butane, can be used for synthesizing alkylated gasoline, also can produce isobutene for dehydrogenation, and then produce polymer; And for example, by C ₅-C ₈the N-alkanes hydrocarbon isomerisation, can be used for production high octane gasoline component etc.The isomerization catalyst H of early application ₂sO ₄although acid strong with HF etc., reaction temperature is low, and strong corrosivity and toxicity are arranged.In the sixties in last century, anhydrous Aluminum chloride is used as isomerization catalyst and uses.Although aluminium chloride is active high, reaction temperature is also lower, selective and poor stability, and same the existence corroded and pollution problem.Afterwards, Ni-SiO ₂-Al ₂o ₃, Pt/Cl-Al ₂o ₃overcome the shortcoming of liquid acid catalyst Deng the introducing of solid heterogeneous catalyst, better active, reaction temperature is lower, but the non-precious metal catalyst poor selectivity, noble metal catalyst is easy to poisoning.In addition, the acidity of catalyst that the aluminium oxide of take is carrier too a little less than, need in course of reaction, constantly add appropriate chloride auxiliary agent to maintain low temperature active, complicated operation.At present, the H-MOR catalyst that contains Pt is widely used industrial catalyst, but it does not overcome above-mentioned shortcoming yet fully.Therefore, the efficient isomerization catalyst of development of new is that the researcher dreams of.

Following patent has disclosed the catalyst of normal alkane isomerization.

Patent CN1465436A(2004.) a kind of catalyst for normal paraffin isomerization and application thereof have been disclosed.It is characterized in that: atom centered by P, Si, W, Mo, V are coordination atom, adopt conventional infusion process preparation, carried heteropoly acid or heteropolyacid salt catalyst.

Patent CN1283668A (2001) has disclosed a kind of alkane hydroisomerization catalyst.It is characterized in that: adopt infusion process, take Pt and Pd as active component, SAPO-11 is the carrier Kaolinite Preparation of Catalyst.

Patent CN1314330A (2001) has disclosed a kind of light normal paraffin catalyst for hydroisomerizing and preparation method thereof.It is characterized in that: take nickel and molybdenum as metal active constituent, the mixture of modenite and boehmite of take is carrier, adopts preparation catalyst.

Patent CN1270990A (2000) has disclosed a kind of preparation method of catalyst for isomerizing light hydrocarbon.It is characterized in that: adopt infusion process that precious metals pt and Pd are carried on the complex carrier that aluminium oxide, Beta zeolite and modenite form and prepare catalyst.

Patent US6080904 (2000) has disclosed the linear paraffin method for hydroisomerization.It is characterized in that: take Pt, W as active component, take ZrO2 as the carrier Kaolinite Preparation of Catalyst.

Patent CN1170632A(1998) disclosed a kind of normal butane isomerization iso-butane catalyst processed.It is characterized in that: with metallic elements such as Ti or Zr, prepare the molecular sieve type ultrastrong acid isomerization catalyst.Carrier is ZSM-5 and ZSM-11 molecular sieve.

Patent US5391532 (1995) has disclosed linear paraffin hydroisomerization reaction method.It is characterized in that: take Pt as active component, take heteropolyacid salt as the carrier Kaolinite Preparation of Catalyst.

Patent CN1076639 (1993) has disclosed a kind of paraffin hydro-isomerized super strong acid catalyzer.It is characterized in that: at H ₂sO ₄under existence, by saturated infusion process, precious metals pt is carried on the mixed oxide or hydroxide carrier of Zr, Fe and Mn.

Patent US5157199 (1992) has disclosed a kind of C ₄-C ₆the reaction method of linear paraffin hydroisomerization.It is characterized in that: with Pt-SO ₄ ²⁺/ ZrO ₂for catalyst.

Patent US5095169 (1992) has disclosed linear paraffin isomerization reaction method.It is characterized in that: take Pt as active component, Beta and MCM-22 molecular sieve are the carrier Kaolinite Preparation of Catalyst.

Patent US5107054 (1992) has disclosed linear paraffin isomerization reaction method.It is characterized in that: take Pt as active component, the Beta molecular sieve is the carrier Kaolinite Preparation of Catalyst.

Patent US5057471 (1991) has disclosed the reaction method of linear paraffin hysomer.It is characterized in that: take Pt as active component, take modenite as the carrier Kaolinite Preparation of Catalyst.

Patent CN86106388(1988) disclosed a kind of preparation method of alkane isomerization catalyst.It is characterized in that: take precious metals pt, Pd is active component, and modenite is carrier, adopts conventional ion exchange process Kaolinite Preparation of Catalyst.

Patent CN86102384A (1986) has disclosed a kind of catalyst of normal alkane isomerization.It is characterized in that: take platinum, palladium and nickel as active component, modenite is carrier, adopts the base exchange method Kaolinite Preparation of Catalyst.

Patent EP0174836 (1986) has disclosed C ₄-C ₆the linear paraffin method for hydroisomerization.It is characterized in that: with Pt-SO ₄ ²⁺/ ZrO ₂for catalyst.

Patent US3032599 (1962) has disclosed C ₄-C ₆the method of linear paraffin hysomer.It is characterized in that: with Pt-SO ₄ ²⁺/ ZrO ₂for catalyst.

Also have a lot of patents to relate to catalyst for normal paraffin isomerization, as:

Relate to platinum, the catalyst patent that palladium is active component: CN102070391A (2011), US7538064B2 (2009), CUS7601881B2 (2009), US7022889B2 (2009), N101242898A (2008), CN101172249A (2008), CN1902149A (2007), US7041866B1 (2006), US2004249230A1 (2004), US2003211937A1 (2003), CN1432550A (2003), CN1345914A (2002), CN1336357A (2002), CN1329585A (2002), CN1249700A (2000), US6080904A (2000), US5707921A (1998), US5654254A (1997), US5591689A (1997), US5658839A (1997), US5557029A (1996), US5463166A (1995), US5182248A (1993), CN1054414A (1991), US5039639A (1991), US5004859A (1991), US5039638A (1991), US5017541A (1991), US49622269A (1990), US4877919A (1989), US4855530A (1989), US4644090A (1987), JP61130241A (1986), US4612293A (1986), US4489216A (1984), US4327240A (1982), US4328385A (1982), US4333856A (1982), US4150060A (1978), US3996249A (1976), US3956413A (1976), US3939102A (1976), US3969425A (1976),

The catalyst patent that to relate to gallium be active component: CN101134171A (2008).

The catalyst patent that to relate to zirconium be active component: CN101171213A (2008), CN101172248A (2008), CN1544400A (2004), CN1194883A (1998), CN1164509A (1997), US4409418A (1983), RU2236291C1.

The catalyst patent that to relate to molybdenum, tungsten be active component: CN1221776A (1999).

The catalyst patent that to relate to titanium be active component: US4400571A (1996), US5536692A (1996).

The catalyst patent that to relate to vanadium be active component: US4118430A (1978).

The catalyst patent that to relate to cobalt be active component: US4830998A (1989), US4085067A (1978), US4075259 (1978).

The catalyst patent that relates to other active component is as follows: US2010080739A1 (2010), US2010191031A1 (2010), US2009069617A1 (2009), US7638675B2 (2009), US7223898B2 (2007), EP1856016A1 (2007), KR20070106590A (2007), AU2006222911A1 (2006), AU2006222911B2 (2006), WO2006099566A1 (2006), US2006205990A1 (2006), RU2264255C1 (2005), US2003114726A1 (2003), US6140547A (2000), US5536895A (1996), US5292988A (1994), US5358919A (1994), US5227554A (1993), US4929799A (1990), US4814544A (1989), GB2167765A (1986), US4404416A (1983), US4400571A (1983), US4404417A (1983), US4347399A (1982), US4324936A (1982), US3946088A (1976), US3761535A (1973), GB1012206A (1965), US3128319A (1964), GB877817A (1961), US2908735A (1959), GB624367A (1949), US2454149A (1948), US2416019A (1947), US2404923A (1946), US2409260A (1946), US2366117A (1944), US2283142A (1942), US2283143 (1942).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 catalyst of normal alkane isomerization.As:

Open source literature petroleum journal 2009(25) 3:345-350 has reported the isomerization of n-hexane on the different molecular sieve catalyst.It is carrier that the document be take SAPO-34, Beta, Y, ZSM-5, ZSM-23, MCM-22, SAPO-11, take Pt as active component, adopts conventional equi-volume impregnating Kaolinite Preparation of Catalyst.Reaction temperature is that 280 ℃, reaction pressure position 2MPa, air speed are to carry out the Isomerization of Hexane reaction under 1h-1 and hydro condition.By height, order on earth is Pt/Beta>Pt/MCM-22>Pt/ZSM-5 (Y) >=Pt/ZSM-23>Pt/SAPO-11 >=PtSAPO-34 to the hexane conversion rate.

The journal 2009(31 of open source literature Wuhan University of Technology) 19:1-3 has reported the hexadecane catalyst for hydroisomerizing.It is complex carrier that the document be take the mixture of tungsten carbide and SAPO-11 molecular sieve, take platinum as active component, adopts preparation catalyst, vacuum drying.The evaluation of catalyst is to carry out on fixed bed high-pressure hydro micro-reactor.

Open source literature chemistry of fuel journal 2005(33) 3:309-313 has reported n-heptane hydroisomerizing catalyst.The document be take SAPO-11 as carrier, take Pt as active component, adopts conventional infusion process to prepare isomerization catalyst.Reaction temperature is 360-380 ℃, and reaction pressure is 0.5MPa-1.0MPa, and air speed is 2.1h ^-1-4.0h ^-1, maximum conversion can reach 66%.

Open source literature catalysis journal 2005(26) 9:750-754 has reported the strong solid acid catalyst of n-heptane isomerization.The document adopts coprecipitation to prepare solid super acid catalyst Pd/WO ₃-ZrO ₂, the normal heptane conversion ratio can reach 70.4%.

Open source literature oil and gas 2004(33) 6:389-396 has reported C ₅/ C ₆the alkane isomerization loaded noble metal catalyst.The document take HY, HUSY and HBeta as molecular sieve be carrier, take Pt and Pd as active component, adopt conventional preparation catalyst.

Open source literature Brazilian Journal of Chemical Engineering2002 (19) 3:335-242 has reported the normal butane isomerization catalyst.It is characterized in that: take HZSM-5 as carrier, take Ga as active component, reaction temperature is 350 ℃, and air speed is 2.5h ^-1.

Open source literature petroleum refining and chemical industry 2001(32) 5:25-28 reported the non-precious metal catalyst of n-pentane isomerization.The document be take the Beta zeolite as carrier, and Ni and Mg are active component, adopts the ion-exchange Kaolinite Preparation of Catalyst.Reaction temperature is 295 ℃, reaction pressure position 2.8MPa, and air speed is 1.5h-1, and hydrogen-oil ratio is 4.0, and reaction-ure conversion-age can reach 68.19%, selective position 94.74%.

Open source literature Applied Catalysis A:General2000 (190): 241-251 has reported the normal butane isomerization catalyst.It is characterized in that: take HM, HBEA and HZSM-5 as carrier, take Pt as active component.

Open source literature petroleum refining and chemical industry 1998(29): 19 have reported C ₅/ C ₆alkane hangs down temp isomerizing catalyst.The document is with Al ₂o ₃for carrier, with AlCl ₃and CCl ₄for chlorinating agent, Pt is active component.Wherein Pt content is 0.35%-0.60%, reaction pressure position 2.0MPa, and reaction temperature is 140 ℃, the charging air speed is 1.0h ^-1, the hexane conversion rate can reach 90%, i-C ₆selectively can reach 30%.

Open source literature petroleum journal 1998(14) 1:52-56 has reported the n-pentane isomerization non-precious metal catalyst.The document be take modenite as carrier, and Ni is the hydrogenation dehydrogenation active component, and Mo is co-catalyst, adopts preparation catalyst.The evaluation of catalyst is to carry out facing on hydrogen fixed bed high-pressure micro-device, and reaction temperature is 300 ℃, and reaction pressure is 2.0MPa, air speed 1.0h-1, and the hydrogen mol ratio is 4.0, and the pentane conversion ratio can reach 67.5%, and isoparaffin is selectively 95%.

In addition, the following discloses document has also been introduced catalyst for normal paraffin isomerization.

To relate to platinum, palladium be active component the following discloses document: the journal 2011(33 of Nanjing University of Technology) 4:1-6; The journal 2011(33 of Nanjing University of Technology) 1:8-13; Petroleum refining and chemical industry 2010(41) 6:1-5; Chemical science and technology market 2010(33) 1:5-7; Chemical progress 2008(20) 5:650-656; Journal of Molecular Catalysis A:2007 (264): 192-201, contemporary chemical industry 2007(36) 5:442-450; Chemical Engineering Journal 2006 (120): 83-89, catalysis journal 2004 (25) 6:431-433; Catalysis journal 2004(25) 8:599-601; Petroleum journal 2004(20) 1:93-98; Oil and gas chemical industry 2004(33) 3:145-151; Applied CatalysisA:General, 2002 (236): 235-243, Applied CatalysisA:General, 2001 (217): 69-78, Microporous and Mesoporous Marerials2001 (42): 245-254, Applied CatalysisA:General.2000 (190): 233-239, Applied CatalysisA:General1998 (169): 137-150, Ind.Eng.Chem.Res.1998 (37): 2592-2600, Journal of Catalysis1997 (170): 96-107, catalysis journal 1980(1) 2:131-137.

What relate to zirconium and be active component has a following discloses document: petroleum journal 2010(supplementary issue) 88-92; Petrochemical industry 2010(39) 1:94-99; Petroleum refining 2010(4): 7-9; Petroleum journal 2009(25) 2:284-290; J.Phys.Chem.B2006 (110): 1711-1721, Topics in Catalysis2005 (35): 9-24, Chem Eur.J.2004 (10): 4750-4754, Applied CatalysisA:General, 2004 (259): 199-205, Henan chemical industry 2004(8): 7-9, Catalysis Letters2002 (78): 1-4.

What relate to molybdenum and be active component has a following discloses document: Industrial Catalysis 2005(13) 4:27-29, Journa of Molecular Catalysis A:2002 (180): 245-258.

What relate to zinc and be active component has a following discloses document: Catalysis Letters1998 (55): 173-176.

To relate to nickel, tungsten be active component the following discloses document: refining and chemical industry 2010(21) 10; Industrial Catalysis 2007(15) 2:22-25; Industrial Catalysis 2004(12) 8:15-18.

What relate to gallium and be active component has a following discloses document: Journal of Molecular CatalysisA:2000 (158): 5-17.

What relate to other active component has a following discloses document: Chemical Manufacture and technology 2011(18) 1:55-58; Catalysis journal 2009(30) 8:705-710; The chemistry of fuel journal, 2008; 36 (2): 160; Petroleum refining and chemical industry 2008(36) 8:2-4; Journal of MolecularCatalysisA2006 (255): 131-158, Chem.Eur.J.2006 (12): 457-465, print during chemical industry, 2005(19) 1:48-50; Chemical industry progress 2005(24) 11:1211-1215; The Chemical Engineer, 2004 (106): 52; The petrochemical industry design, 2004,21 (3) 1-5; Catalysis journal 2004(25) 6:431-433; Oil Refining Technologies and engineering 2004(34) 12:1-4; Applied CatalysisA:General2003 (256): 243-250, Applied CatalysisA:General2002 (235): 113-123, the journal 2001(22 of Qingtao Chemical Engineering College) 4:312-315, Catalysis Letters1997 (43): 7-10, J.Chem.SOC.Faraday Trann.1995 (91) 2:367-373, Applie CatalysisA:General2000 (198): 81-93, J.Phys.Chem.1992 (96): 1051-1060.

In alkane isomerization reaction, need to there is the acid catalyst of strong acid center, take sulfuric acid, hydrofluoric acid, aluminium chloride and trichloride antimony during as catalyst, can cause metal erosion and contaminated environment.During with the solid acid catalyst of supporting Pt and halogens, very responsive to water, reaction raw materials needs strict dehydration.With SO ₄ ^2-/ ZrO ₂during for the solid super acid catalyst of representative, existence and stability is poor, and inactivation is fast, easily the shortcoming such as carbon distribution.Therefore, the efficient catalyst of development of new is necessary.

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; The one, golden precursor is loaded to infusion process and deposition-precipitation method on the carrier prepared in advance.The preparation method of early stage load type gold catalyst infusion process commonly used.It is lower that infusion process is generally used for preparing active component content, and need the catalyst of sufficient mechanical strength.By the preparation process of the method nano catalyst, be, at first by carrier impregnation in containing in golden salting liquid, and then carry out drying, roasting and reduction processing, method is simple.It is carrier that infusion process can be selected various metal or nonmetal oxide and molecular sieve etc.The commonly used golden precursor for preparing nano catalyst is gold chloride (HAuCl ₄.3H ₂o) and chlorauride (AuCl ₃) and gold complex KAu (CN) ₂[Au (en) ₂] Cl ₃(en is ethylenediamine) etc.

Coprecipitation 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 precipitating reagent, then carry out standing, filtration, washing, drying and high-temperature roasting and process.The advantage of coprecipitation is that preparation is reproducible, and shortcoming is that the part gold grain can be buried in carrier inside, and the utilization rate of gold is low, is not suitable for the carriers such as titanium oxide, zeolite molecular sieve.When the application precipitation method, the control of pH value is technological difficulties.

Deposition-the precipitation method are also supported catalyst preparation methods commonly used, and it has the advantage of infusion process and the precipitation method concurrently.The canonical process for preparing Au catalyst by the deposition-precipitation method is: by metal or nonmetal oxide and molecular sieve etc. in carrier joins golden precursor solution, under certain reaction temperature, continuous stirring also dropwise adds precipitating reagent, solution reaction is carried out under suitable pH value, until precipitation fully.And then solid content is carried out to sedimentation, filtration, washing, drying, roasting or activation process.

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 activity, 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 construction of take is carrier, and carrying method is deposition-precipitation method, loads under normal pressure and carries out, and take gold chloride 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, gold chloride is presoma, and carrying method is conventional infusion 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 aluminium oxide, silica, pottery, TiO ₂deng being carrier, gold chloride is golden presoma, and carrying method is infusion 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 ferric nitrate as the co-precipitation carrier, the chloric acid gold is presoma, take sodium carbonate as precipitating reagent, and carrying method is coprecipitation, 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, be carrier, the chloric acid gold is presoma, and carrying method is infusion 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 carrier: 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 adsorption capacities, 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 CatalA:Gen, 291 (2005) 162 have reported a kind of method for preparing load gold catalyst.Its technical characterictic is: take Y, β and modenite as carrier, with HAuCl ₄for golden presoma, with NaOH, be precipitating reagent, 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 modenite as carrier, with HAuCl ₄for golden presoma, with NaOH, be precipitating reagent, 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 precipitating reagent, 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 precipitating reagent, 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.Precipitating reagent is urea, TiO ₂for carrier.The disclosure document adopts TiO ₂for carrier and urea are precipitating reagent, 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 precipitating reagent, 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 distinct methods and different oxide 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 catalyst 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 catalyst.

The present invention utilizes the negative pressure deposition-precipitation method to prepare load type gold catalyst, has that metal dispersity is high, gold grain is little, the processing time is short and characteristics such as saboteur's sieve skeleton shelf structure not.We find through research, the catalyst prepared by the method, as the novel supported Au catalyst of alkane isomerization, has reactivity high, stability and selectively good, and there is unique acidity, non-corrosiveness and environmental pollution, be easy to the characteristics of preparation and regeneration.

Summary of the invention

The invention provides a kind of load type nano gold catalyst and produce the method for isoparaffin for alkane isomerization.Alkane isomerization should be used metal-sour bifunctional catalyst.

While being carried on silica-rich zeolite by this method by nm of gold, gold can with silica-rich zeolite generation strong interaction, thereby form the nanogold particle of high dispersive.And due to the polarization of Au, forming process acid when Au and carrier function.Also there is metallicity by the gold of load simultaneously, thereby formed metal-sour bifunctional catalyst.We find by research; the carrying method of Au is very important; after molecular sieve is carried out to sufficient negative pressure degasification purified 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 precipitating reagent, reaction temperature 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 course of reaction 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 inner 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 silica-rich 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, modenite 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, precipitating reagent 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 alkane isomerization and metal active center, can make n-alkane under the difunctional effect of metal and carrier, dehydrogenation generates alkene, alkene obtains proton and forms carbonium ion on acid site, and carbonium ion carries out skeletal isomerization and add hydrogen desorption generating isoparaffin again.

Technical scheme of the present invention is as follows:

1. the preparation of load gold catalyst

The first step, carry out pretreatment to the silica-rich zeolite carrier.

(1). the zeolite that the silica alumina ratio of said silica-rich zeolite is 10～∞, as ZSM-5, ZSM-8, ZSM-11, MCM-22, MCM-49, MCM-56, ITQ-2 and ZSM-12, beta-zeolite, modenite, TS-1 and pure silicon zeolite or through above-mentioned zeolite metal-modified and that additive method was processed.The grain size of zeolite is between 5nm ~ 30 μ m.The silica-rich zeolite carrier is carried out to calcination process.Sintering 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 Chemistry12 (2002) 369-373, Journal of Molecular Catalysis B:Enzymatic22 (2003) 119 – 133, Journal of Catalysis255 (2008) 68 – 78.The engineer who is familiar with this area all can adopt the technical 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, with deionized water washing, 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, ammonium carbonate etc., ammonium salt solution concentration is 0.05 ~ 1.0mol/L, the liquid-solid volume ratio of catalyst 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 baking temperature, 1 ~ 100 hour drying time; Due to NH ₄ ⁺→ NH ₃+ H ⁺middle NH ₃with proton H ⁺between strong complexing power, require roasting process to need fully, so sintering temperature selects 300 ~ 700 ° of C, preferred 400 ~ 600 ° of C; Roasting time is 4 ~ 20 hours, preferably 3 ~ 8 hours.Said Na ⁺the assay method of content can adopt flame photometer, Inductively Coupled Plasma(ICP) measured.The engineer who is familiar with this area can carry out Na with reference to specification ⁺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 the deionized water washing, drier, roasting obtains catalyst.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 catalyst ~ 20:1, preferably 3:1 ~ 10:1; The acid reaming processing time is 30min ~ 100 hour, preferably 1 ~ 5 hour; Treatment temperature is 20 ~ 80 ° of C.Baking temperature is 50 ~ 200 ° of C, and be 3 ~ 20 hours drying time, and sintering 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 diffusion rate in duct.In fact the hydrogen type catalyst obtained after the ammonium exchange just can directly be used as catalyst.But sour reaming is to being conducive to improve the activity of catalyst.

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 purified treatment under uniform temperature through pretreated Hydrogen silica-rich zeolite carrier.Then under fully stirring, first use golden precursor solution contact carrier, and then add precipitating reagent to pass through negative pressure deposition sedimentation reaction load gold in mixture.The negative pressure degasification treatment temperature is 20～90 ℃, and the degassed time is 0.5～20 hour, range of negative pressure is-0.01～-0.1MPa.Although higher vacuum is favourable to purifying, can increase the catalyst cost of manufacture.Said golden precursor is HAuCl ₄, said precipitating reagent 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 reaction temperature, optional 5～100 hours of mixing time.

(4). the sediment to gold-supported carries out post processing: comprise Separation of Solid and Liquid, wash extremely without Cl by deionized water ^-, and drying and the roasting of solid content.Wherein, optional 80～200 ℃ of baking temperature, optional 0.5～100 hour of drying time.The optional electric furnace of the roasting of catalyst (Muffle furnace) roasting, also can select the plasma roasting, optional 200 ℃～600 ℃ of sintering 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 infusion process load the second active component.

(1). with infusion 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 purified treatment at a certain temperature.Then under fully stirring, by negative pressure impregnation method load the second metal.The negative pressure degasification treatment temperature is 20～90 ℃, and the degassed time is 0.5～20 hour, pressure is not less than～-0.1MPa.Although higher vacuum is favourable to purifying, can increase the catalyst 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 mixing time.

(2) solid content is carried out to post processing: comprise Separation of Solid and Liquid, and the drying of solid content and roasting.Wherein, optional 80～200 ℃ of baking temperature, optional 0.5～100 hour of drying time.The optional electric furnace of the roasting of catalyst (Muffle furnace) roasting, also optional plasma roasting, optional 200 ℃～600 ℃ of sintering temperature, optional 0.5～100 hour of roasting time, the optional air of calcination atmosphere, nitrogen, helium, argon gas or oxygen.

2. the normal alkane isomerization reactivity worth of catalyst is estimated.

Said alkane can be high-purity n-alkane, can be normal butane, pentane, n-hexane, normal heptane, normal octane, and any mixture; Can contain alkene in raw material, also can contain and be less than C ₄light component and be greater than C ₈heavy constituent, light component and heavy constituent consist of alkane and alkene; Typical raw material comprises reforming raffinate oil, reforming topped oil, light naphthar, various straight(-run) tops, lightweight condensate.Reaction can and have in the carrier gas situation at no carrier gas to be carried out, and described carrier gas is H ₂, N ₂, CO2, CH ₄, C ₂h ₆in one or two or more kinds mixture, carrier gas/hydrocarbon volume ratio is 0～100;

(1) carry out normal alkane isomerization on fixed bed reactors: catalyst adopts conventional extruded moulding, and reaction temperature is 100 ~ 800 ° of C, preferred 150 ~ 600 ° of C, and reaction pressure normal pressure ~ 10MPa, preferred 0.3 ~ 3.0MPa, weight space velocity is 0.5 ~ 20h ^-1.

(2) carry out normal alkane isomerization on moving-burden bed reactor: catalyst adopts conventional wear-resisting bead, and reaction temperature is 100 ~ 800 ° of C, preferred 150 ~ 600 ° of C, and reaction pressure is 0.1 ~ 0.5MPa, weight space velocity is 0.5 ~ 20h ^-1.

(3) carry out normal alkane isomerization on fluidized-bed reactor: catalyst adopts the mist projection granulating moulding, and particle size range is the 20-120 micron.Reaction temperature is 100 ~ 800 ° of C, preferred 150 ~ 600 ° of C, and reaction pressure is 0.1 ~ 0.3MPa, agent hydrocarbon ratio is 0.5 ~ 5.

The invention has the beneficial effects as follows the advantage such as the load gold catalyst prepared by the method has that the preparation method is simple, gold particle high dispersive, gold grain are little.Can obtain metal-sour bifunctional molecule sieve catalyst.

Therefore this catalyst, for isomerization reaction, has activity high, the advantage that reaction temperature is low.

The specific 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 normal butane isomerization and produce iso-butane on fixed bed reactors.

(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, with deionized water washing, 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 baking temperatures, 12 hours drying times, sintering 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 the deionized water washing, 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 processing time is 24 hours, treatment temperature is 30 ℃.Baking temperature is 110 ℃, and be 12 hours drying time, and sintering temperature selects 540 ℃, and roasting time is 3 hours, obtains the HZSM-5 zeolite catalyst.This catalyst is carried out to NH ₃-TPD and infrared spectrum acidity characterize.

(4) by 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 normal butane, and normal butane purity is 99.5%, and the charging air speed is 1.0h ^-1, reaction temperature is 350 ℃, reaction is carried out under no carrier gas and normal pressure.The reaction procatalyst is used nitrogen blowing 30 minutes under reaction temperature, is then reacted, and reacts sample analysis after 4 hours.N-butane conversion is 25%, and iso-butane is selectively 30%.

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, by deionized water, wash neutrality, 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 catalyst 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 baking temperature, 12 hours drying times, sintering 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 the deionized water washing, drier, roasting obtains catalyst.Said acid is HNO ₃.Acid concentration is 0.6mol/L, the liquid-solid volume ratio 5:1 of acid solution and catalyst, and the sour reaming processing time is 24 hours, treatment temperature is 30 ℃.Baking temperature is 110 ° of C, and be 12 hours drying time, and sintering 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 catalyst.But sour reaming is to being conducive to improve the activity of catalyst.

(4). with negative pressure deposition-precipitation method gold-supported: will carry out the negative pressure degasification purified treatment under uniform temperature through pretreated Hydrogen silica-rich zeolite carrier.Then under fully stirring, first use golden precursor solution contact carrier, and then add precipitating reagent 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 pretreatment.The negative pressure degasification treatment temperature is 80 ℃, and the degassed time is 5 hours, and range of negative pressure is-0.05MPa.Said golden precursor is HAuCl ₄, said precipitating reagent is for analyzing 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 reaction temperature is 80 ℃, and mixing time is 20 hours.After stirring stops standing 4 hours again.

(5). the solid content to gold-supported carries out post processing: comprise Separation of Solid and Liquid, wash extremely without Cl by deionized water ^-, and drying and the roasting of solid content.Wherein, optional 100 ℃ of baking temperature, 12 hours drying times, 400 ℃ of sintering temperatures, roasting time 4 hours, calcination atmosphere is air.Obtain the support type Au/HZSM-5 zeolite molecular sieve catalyst 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, sintering 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 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, sintering 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 is changed into-0.06MPa, the chlorauric acid solution consumption is 41.86ml, sintering 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 roasting, sintering temperature changes respectively 200 ℃, 300 ℃, 400 ℃, 500 ℃, 600 ℃ into, and calcination atmosphere is nitrogen.Obtain the load type gold catalyst after the different temperatures 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 mixing time of soluble solids into 1～24 hour, obtain 1.0Au/HZSM-5 and the 2.0%Au/HZSM-5 catalyst of different mixings 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 collaurum can arrive nucleation site.Along with the prolongation of mixing 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, significant change will no longer occur in the particle diameter of gold particle.Optimum mixing time is 18～20 hours.The gold grain that is less than 10nm is 60～70%.

Embodiment 9:

Repeat embodiment 1, but vacuum is changed into respectively-0.01MPa ,-0.03MPa ,-0.05MPa ,-0.07MPa ,-1.0MPa.Obtain the load type gold catalyst of different vacuums.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 sintering 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 sintering 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 is-0.05MPa, and the chlorauric acid solution consumption is 10.46ml, and sintering 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 is-0.06MPa, and the chlorauric acid solution consumption is 20.93ml, and sintering 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 is-0.05MPa, and the chlorauric acid solution consumption is 41.86ml, and sintering 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 is-0.05MPa, and the chlorauric acid solution consumption is 15.70ml, and sintering 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 is-0.05MPa, and the chlorauric acid solution consumption is 10.46ml, and sintering 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 is-0.045MPa, and the chlorauric acid solution consumption is 6.28ml, and sintering 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 is-0.04MPa, and the chlorauric acid solution consumption is 6.28ml, and sintering 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 is-0.04MPa, and the chlorauric acid solution consumption is 6.28ml, and sintering 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 precipitating reagent consumption into 10g, vacuum is-0.04MPa that sintering 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 precipitating reagent consumption into 3g, vacuum is-0.04MPa that sintering temperature is 400 ℃.Obtain the 2.0%Au/HZSM-5 catalyst.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, by deionized water, wash neutrality, 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 catalyst 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 baking temperature, 12 hours drying times, sintering 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 the deionized water washing, drier, roasting obtains catalyst.Said acid is HNO ₃.Acid concentration is 0.6mol/L, the liquid-solid volume ratio 5:1 of acid solution and catalyst, and the sour reaming processing time is 24 hours, treatment temperature is 30 ℃.Baking temperature is 110 ° of C, and be 12 hours drying time, and sintering 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 catalyst.But sour reaming is to being conducive to improve the activity of catalyst.

(4) with negative pressure deposition-precipitation method gold-supported: will carry out the negative pressure degasification purified treatment under uniform temperature through pretreated Hydrogen silica-rich zeolite carrier.Then under fully stirring, first use golden precursor solution contact carrier, and then add precipitating reagent 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 pretreatment.The negative pressure degasification treatment temperature is 80 ℃, and the degassed time is 5 hours, and range of negative pressure is-0.05MPa.Said golden precursor is HAuCl ₄, said precipitating reagent is for analyzing 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 reaction temperature is 80 ℃, and mixing 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 purified treatment at a certain temperature.Then under fully stirring, by negative pressure impregnation method load the second metal.The negative pressure degasification treatment temperature is 80 ℃, and the degassed time is 4 hours, and range of negative pressure is-0.45MPa.Although higher vacuum is favourable to purifying, can increase the catalyst 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 mixing time.

(6). the bimetallic solid content of load regulation is carried out to post processing: comprise Separation of Solid and Liquid, with drying and the roasting of deionized water washing and solid content.Wherein, optional 100 ℃ of baking temperature, 12 hours drying times, 400 ℃ of sintering temperatures, roasting time 4 hours, calcination atmosphere is air.Obtain the support type Au-Zn/HZSM-5 zeolite molecular sieve catalyst 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.Sintering 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 load 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.Sintering 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 catalyst in embodiment 23 under nitrogen atmosphere plasma roasting, sintering 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 catalyst in embodiment 23 is changed successively into to any one of helium, argon gas, air, oxygen atmosphere, roasting apparatus changes the plasma roasting into, sintering 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 size is 5 μ m as follows, and the consumption of change urea precipitating reagent, 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 waterglass 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 size is 10 μ m with the following method changes the precipitating reagent 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 waterglass and be diluted with water to B solution.Then, under vigorous stirring, A solution and the absolute ethyl 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 normal alkane isomerization and produce isoparaffin on fixed bed reactors.

By boehmite extruded moulding according to a conventional method for the A-1 catalyst sample of above-mentioned preparation, the zeolite catalysis agent content is 80%, and the reaction time catalizer loadings is 2g, and raw material is normal butane, and normal butane purity is 99.5%, and the charging air speed is 1.0h ^-1, reaction temperature is 350 ℃, reaction is carried out under no carrier gas and normal pressure.The reaction procatalyst is used nitrogen blowing 30 minutes under reaction temperature, is then reacted, and reacts sample analysis after 4 hours.N-butane conversion is 35%, and iso-butane is selectively 75%.

Embodiment 34:

Repeat embodiment 33, but change reaction raw materials into pentane and n-hexane mixture, its pentane and n-hexane proportioning are 40%:60%, and feed stock conversion is 58%, and research octane number (RON) (RON) is 81.3.

Execute example 35:

Repeat embodiment 33, but change reaction raw materials into pentane and n-hexane mixture, its pentane and n-hexane proportioning are 60%:40%, and feed stock conversion is 58%, and research octane number (RON) (RON) is 81.3.

Embodiment 36:

Repeat embodiment 33, but change reaction raw materials into mixed butanes, its normal butane and iso-butane proportioning are 85%:15%, and feed stock conversion is 58%, and research octane number (RON) (RON) is 81.3.

Embodiment 37:

Repeat embodiment 33, but change reaction raw materials into mixed butanes, its normal butane and iso-butane proportioning are 15%:85%, and reaction temperature is 400 ℃, and n-butane conversion is 25%, and iso-butane is selectively 65%.

Embodiment 38:

Repeat embodiment 33, but change reaction raw materials into mixed butanes, its normal butane and iso-butane proportioning are 30%:70%, and reaction temperature is 400 ℃, and n-butane conversion is 30%, and iso-butane is selectively 87%.

Embodiment 39:

Repeat embodiment 33, but be normal butane, pentane and n-hexane mixture by reaction raw materials, wherein, normal butane weight is 15%, pentane weight is 33%, and n-hexane weight is 52%, and feed stock conversion is 65%, and research octane number (RON) (RON) is 80.5.

Embodiment 40:

Repeat embodiment 33, but be C5 and C6 distillate by raw material, its distillate is pressed the 1.5:1 weight ratio and is mixed, and reaction temperature is 300 ℃, and feed stock conversion is 55%, and research octane number (RON) (RON) is 70.

Embodiment 41:

Repeat embodiment 33, but be pentane and n-hexane mixture by reaction raw materials, wherein, pentane weight is 60%, and n-hexane weight is 40%, and catalyst changes A-4 into, and reaction temperature is 400 ℃, and feed stock conversion is 63%, and research octane number (RON) (RON) is 86.

Embodiment 42:

Repeat embodiment 33, but change reaction raw materials into mixed butanes, its normal butane and iso-butane proportioning are 85%:15%, and catalyst is A-3, and n-butane conversion is 65%, and iso-butane is selectively 95%.

Embodiment 43:

Repeat embodiment 33, but change reaction raw materials into mixed butanes, its normal butane and iso-butane proportioning are 15%:85%, and catalyst is A-3, and reaction temperature changes 400 ℃ into, and n-butane conversion is 25%, and iso-butane is selectively 65%.

Embodiment 44:

Repeat embodiment 33, but change reaction raw materials into mixed butanes, its normal butane and iso-butane proportioning are 30%:70%, and catalyst is A-4, and reaction temperature changes 400 ℃ into, and n-butane conversion is 30%, and iso-butane is selectively 87%.

Embodiment 45:

Repeat embodiment 33, but change reaction raw materials into normal butane, pentane and n-hexane mixture, wherein, normal butane weight is 15%, pentane weight is 33%, and n-hexane weight is 52%, and catalyst changes A-6 into, feed stock conversion is 65%, and research octane number (RON) (RON) is 80.5.

Embodiment 46:

Repeat embodiment 33, but change reaction raw materials into C5 and C6 distillate, its distillate is pressed the 1.5:1 weight ratio and is mixed, and catalyst changes A-7 into, and reaction temperature changes 300 ℃ into, and feed stock conversion is 55%, and research octane number (RON) (RON) is 70.

Embodiment 47:

Repeat embodiment 33, but change reaction raw materials into normal butane, pentane and n-hexane mixture, wherein, normal butane weight is 15%, pentane weight is 33%, n-hexane weight is 52%, and catalyst changes A-8 into, and reaction temperature changes 400 ℃ into, the raw material total conversion 60%, and research octane number (RON) (RON) is 83.5.

Embodiment 48:

Repeat embodiment 33, but change reaction raw materials into C5 and C6 distillate, its distillate is pressed the 2:1 weight ratio and is mixed, and catalyst changes A-9 into, and reaction temperature changes 400 ℃ into, and the raw material total conversion is 64%, and research octane number (RON) (RON) is 73.5.

Embodiment 49:

Repeat embodiment 33, but change reaction temperature into 400 ℃, catalyst changes A-11 into, and n-butane conversion is 38%, and iso-butane is selectively 59%.

Embodiment 50:

Repeat embodiment 33, but change reaction raw materials into pentane, pentane purity is 99%, and catalyst changes A-1 into, and raw material carries out hydroisomerization reaction, and reaction temperature changes 300 ℃ into, hydrogen/oil mol ratio 4.0, and hydrogen purity is 99.99%.The pentane yield is 65.50%, and isopentane is selectively 97%.

Embodiment 51:

Repeat embodiment 33, but change reaction raw materials into pentane, pentane purity is 99%, and catalyst changes A-2 into, and raw material carries out hydroisomerization reaction, and reaction temperature changes 300 ℃ into, hydrogen/oil mol ratio 4.0, and hydrogen purity is 99.99%.The pentane yield is 65.50%, and isopentane is selectively 97%.

Embodiment 52:

Repeat embodiment 33, but change reaction raw materials into n-hexane, n-hexane purity is 99%, and catalyst changes A-1 into, carries out the non-hydro isomerizaiton reaction, and reaction temperature changes 300 ℃ into.The hexane conversion rate is that 75.50%, 2,2-dimethylbutane is selectively 97%.

Embodiment 53:

Repeat embodiment 33, but change reaction raw materials into normal heptane, normal heptane purity is 99%, and raw material carries out hydroisomerization reaction, and catalyst changes A-1 into, and reaction temperature changes 250 ℃ into, hydrogen/oil mol ratio 8.0, and hydrogen purity is 99.99%.Product take methyl hexane, dimethyl pentane and triptane as.The normal heptane conversion ratio is 89.50%, and methyl hexane, dimethyl pentane and triptane overall selectivity are 97%.

Embodiment 54:

Repeat embodiment 33, but change reaction raw materials into pentane, pentane purity is 99%, and catalyst changes A-2 into, and raw material carries out hydroisomerization reaction, and reaction temperature changes 300 ℃ into, hydrogen/oil mol ratio 4.0, and hydrogen purity is 99.99%.The pentane yield is 65.50%, and isopentane is selectively 97%.

Embodiment 55:

Repeat embodiment 33, but change reaction raw materials into pentane, pentane purity is 99%, and catalyst changes A-2 into, and raw material carries out hydroisomerization reaction, and reaction temperature changes 300 ℃ into, hydrogen/oil mol ratio 4.0, and hydrogen purity is 99.99%.The pentane yield is 65.50%, and isopentane is selectively 97%.

Embodiment 56:

Repeat embodiment 33, but change reaction raw materials into n-hexane, n-hexane purity is 99%, and catalyst changes A-2 into, carries out the non-hydro isomerizaiton reaction, and reaction temperature changes 300 ℃ into.The hexane conversion rate is that 75.50%, 2,2-dimethylbutane is selectively 97%.

Embodiment 57:

Repeat embodiment 33, but change reaction raw materials into normal heptane, normal heptane purity is 99%, and raw material carries out hydroisomerization reaction, and catalyst changes A-2 into, and reaction temperature changes 250 ℃ into, hydrogen/oil mol ratio 8.0, and hydrogen purity is 99.99%.Product take methyl hexane, dimethyl pentane and triptane as.The normal heptane conversion ratio is 89.50%, and methyl hexane, dimethyl pentane and triptane overall selectivity are 97%.

Embodiment 58:

Repeat embodiment 33, but change reaction raw materials into pentane and n-hexane mixture, its pentane and n-hexane proportioning are 40%:60%, and catalyst changes A-19 into, and feed stock conversion is 58%, and research octane number (RON) (RON) is 81.3.

Execute example 59:

Repeat embodiment 33, but change reaction raw materials into pentane and n-hexane mixture, its pentane and n-hexane proportioning are 60%:40%, and catalyst changes A-19 into, and feed stock conversion is 58%, and research octane number (RON) (RON) is 81.3.

Embodiment 60:

Repeat embodiment 33, but change reaction raw materials into pentane, pentane purity is 99%, and catalyst changes A-19 into, and raw material carries out hydroisomerization reaction, and reaction temperature changes 300 ℃ into, hydrogen/oil mol ratio 4.0, and hydrogen purity is 99.99%.The pentane yield is 65.50%, and isopentane is selectively 97%.

Embodiment 61:

Repeat embodiment 33, but change reaction raw materials into pentane, pentane purity is 99%, and catalyst changes A-20 into, and raw material carries out hydroisomerization reaction, and reaction temperature changes 300 ℃ into, hydrogen/oil mol ratio 4.0, and hydrogen purity is 99.99%.The pentane yield is 65.50%, and isopentane is selectively 97%.

Embodiment 62:

Repeat embodiment 33, but change reaction raw materials into n-hexane, n-hexane purity is 99%, and catalyst changes A-21 into, carries out the non-hydro isomerizaiton reaction, and reaction temperature changes 300 ℃ into.The hexane conversion rate is that 76.50%, 2,2-dimethylbutane is selectively 98%.

Embodiment 63:

Repeat embodiment 33, but change reaction raw materials into normal heptane, normal heptane purity is 99%, and raw material carries out hydroisomerization reaction, and catalyst changes A-22 into, and reaction temperature changes 250 ℃ into, hydrogen/oil mol ratio 8.0, and hydrogen purity is 99.99%.Product take methyl hexane, dimethyl pentane and triptane as.The normal heptane conversion ratio is 90.50%, and methyl hexane, dimethyl pentane and triptane overall selectivity are 98%.

Embodiment 64:

Repeat embodiment 33, but change reaction raw materials into pentane, pentane purity is 99%, and catalyst changes A-23 into, and raw material carries out hydroisomerization reaction, and reaction temperature changes 300 ℃ into, hydrogen/oil mol ratio 4.0, and hydrogen purity is 99.99%.The pentane yield is 91%, and isopentane is selectively 98%.

Embodiment 65:

Repeat embodiment 33, but change reaction raw materials into pentane, pentane purity is 99%, and catalyst changes A-24 into, and raw material carries out hydroisomerization reaction, and reaction temperature changes 300 ℃ into, hydrogen/oil mol ratio 4.0, and hydrogen purity is 99.99%.The pentane yield is 688%, and isopentane is selectively 98%.

Embodiment 66:

Repeat embodiment 33, but change reaction raw materials into n-hexane, n-hexane purity is 99%, and catalyst changes A-25 into, carries out the non-hydro isomerizaiton reaction, and reaction temperature changes 300 ℃ into.The hexane conversion rate is that 76.50%, 2,2-dimethylbutane is selectively 97.5%.

Embodiment 67:

Carry out n-pentane isomerization and produce isopentane 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 1000g is proceeded in small-sized movable bed testing equipment, and reaction raw materials is pentane, and concentration is 99.5%, and reaction temperature is 350 ℃, and the agent hydrocarbon is than 1:1, and the charging air speed is 0.5h ^-1, reaction is carried out at no carrier gas and normal pressure.The reaction procatalyst is used nitrogen blowing 30 minutes under reaction temperature, is then reacted.The pentane conversion ratio is 87%, and isopentane is selectively 74%.

Embodiment 68:

Carry out n-pentane isomerization and produce isopentane on fluidized-bed reactor.

The A-20 catalyst sample of above-mentioned preparation is made to the powder of 20 ~ 120 microns by the conventional mist projection granulating method of forming.The wear-resisting pellet catalyst of 1000g is proceeded in small sized flow bed testing equipment, and raw material is pentane, and concentration is 99.5%, and the agent hydrocarbon is than 1:1, and reaction temperature is 350 ℃, and reaction is carried out under no carrier gas and 0.2MPa pressure.The reaction procatalyst is used nitrogen blowing 30 minutes under reaction temperature, is then reacted.The pentane conversion ratio is 82%, and isopentane is selectively 75%.

Claims (7)

1. the molecular sieve catalyst with gold-supported transforms the method that n-alkane is isoparaffin, it is characterized in that comprising the steps:

A. the silica-rich zeolite carrier is carried out to pretreatment

(1) the silica-rich zeolite carrier is carried out to calcination process, sintering temperature selects 400 ~ 600 ℃, and roasting time is 3 ~ 8 hours; The silica alumina ratio of silica-rich zeolite is greater than 10, and the grain size 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 with deionized water washing, then carry out drying and calcination process obtains h-type zeolite; 80 ~ 200 ℃ of baking temperatures, 1 ~ 100 hour drying time; 400 ~ 600 ℃ of sintering 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 the deionized water washing, 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 processing time is 1 ~ 5 hour, treatment temperature is 20 ~ 80 ℃; Baking temperature is 50 ~ 200 ℃, and be 3 ~ 20 hours drying time; Sintering 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 purified treatment through pretreated h-type zeolite carrier, treatment temperature 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 precipitating reagent to pass through negative pressure deposition sedimentation reaction load gold in mixture, the reaction time is 5～100 hours;

(2) sediment of gold-supported carried out to post processing: comprise Separation of Solid and Liquid, wash extremely without Cl by deionized water ^-, the drying of solid content and roasting; 80～200 ℃ of baking temperatures, 0.5～100 hour drying time; 300 ~ 700 ℃ of sintering temperatures; Roasting time 3 ~ 20 hours; Muffle furnace or plasma roasting are selected in the roasting of catalyst, and calcination atmosphere selects nitrogen, helium, argon gas, air or oxygen;

C. normal alkane isomerization on reactor

(1) carry out normal alkane isomerization on fixed bed reactors: catalyst adopts conventional extruded moulding, and reaction temperature is 150 ~ 600 ° of C, and reaction pressure is 0.3 ~ 3.0MPa, and weight space velocity is 0.5 ~ 20h ^-1;

(2) carry out normal alkane isomerization on moving-burden bed reactor: catalyst adopts conventional wear-resisting bead, and reaction temperature is 150 ~ 600 ° of C, and reaction pressure is 0.1 ~ 0.5MPa, and weight space velocity is 0.5 ~ 20h ^-1;

(3) carry out normal alkane isomerization on fluidized-bed reactor: catalyst adopts the mist projection granulating moulding, and particle size range is the 20-120 micron; Reaction temperature is 150 ~ 600 ° of C, 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, described silica-rich zeolite refers to ZSM-5, ZSM-8, ZSM-11, MCM-22, MCM-49, MCM-56, ITQ-2, ZSM-12, beta-zeolite, modenite, TS-1 or pure silicon zeolite.

3. method according to claim 1, is characterized in that described golden precursor is HAuCl ₄, 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 precipitating reagent is urea, by precipitating reagent regulator solution pH value, is 4～9.

5. according to claim 1,2,3 or 4 described methods, it is characterized in that on the catalyst of gold-supported with infusion process load the second metal: the negative pressure degasification treatment temperature is 20～90 ℃, and 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, dip time 0.5-24 hour; The bimetallic solid content of load regulation is carried out to post processing: comprise Separation of Solid and Liquid, the drying of solid content and roasting; Baking temperature is 50 ~ 200 ℃, and be 3 ~ 20 hours drying time; Sintering temperature selects 300 ~ 700 ℃; Roasting time is 3 ~ 20 hours; The roasting of catalyst is Muffle furnace or plasma roasting, and calcination atmosphere selects nitrogen, helium, argon gas, air or oxygen.

6. method according to claim 1, is characterized in that described reaction raw materials is one or two or more kinds mixture in normal butane, pentane, n-hexane, normal heptane, normal octane, or the C after oil gas field production ₄cut, C ₅～C ₁₀any C of cut, Petrochemical Enterprises by-product ₄cut, low-octane C ₅～C ₈cut.

7. method according to claim 5, it is characterized in that described counter be to carry out under carrier gas exists, 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.