CN101747135A - Method for producing low-carbon alkene by catalytic pyrolysis of biomass - Google Patents
Method for producing low-carbon alkene by catalytic pyrolysis of biomass Download PDFInfo
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Abstract
A method for producing low-carbon alkene by catalytic pyrolysis of biomass comprises: contacting biomass raw material or raw material containing biomass and hydrocarbon oil with catalyst containing five-membered ring high-silicon zeolite in a lifting pipe or fluidized bed reactor, and then reacting under catalytic pyrolysis condition; separating reaction product and unborn catalyst; separating the product after the reaction product is fed in a subsequent separating system so as to obtain liquid product and gas product containing ethylene and propylene, returning the unborn catalyst in the reactor for cycle use after stripping and regenerating, wherein the five-membered ring high-silicon zeolite contains phosphorus and transition metal, and the catalytic pyrolysis conditions are as follows: the reaction temperature is 550-700 DEG C, the weight ratio of catalyst to raw material oil is 6-40, diluent gas is added in the reaction process, and the weight ratio of diluent gas to raw material is 0.1-1: 1. The method is used for producing low-carbon alkene by transformation of biomass raw material, and has relatively higher low-carbon alkene yield.
Description
Technical field
The present invention relates to a kind of method of utilizing of biomass material, relate to a kind of method of utilizing the biomass material producing low-carbon alkene by catalytic pyrolysis furtherly.
Background technology
Ethene more than 95%, propylene are produced the low-carbon alkene technology by naphtha steam cracking and heavy-oil catalytic and are provided in the market.Heavy-oil catalytic thermal cracking is produced the low-carbon alkene technology, utilizes heavy oil to produce low-carbon alkenes such as ethene, propylene, and it is low to have energy consumption, ingredient requirement is low, and product profile adjustment flexible characteristic is because the gradual change of crude oil day is heavy, change is bad, this technology comes into one's own day by day, has vast potential for future development.
Along with becoming gradually, petroleum heavily becomes the day by day exhausted of bad and petroleum resources, the substitute of processing oil has caused extensive concern, and for example WO2004016572, WO2005016856 and CN02152480.7 provide and add for example method of organic oxygen-containing compounds production alkene such as methyl alcohol, ethanol, dme, diethyl ether or its mixture of low-carbon alcohol, ether compound in the hydrocarbon oil catalytic cracking raw material.And as a kind of reproducible resource, the processing and utilization of biomass examples such as vegetable and animals oils and rubbish oil is subjected to paying close attention to widely in recent years.
CN200610112924.6 discloses a kind of method processing animal and vegetable oil and rubbish oil that utilizes catalytic cracking, in the hope of producing the production technology of light-end products and ethene and propylene.This technology has been used the HZSM-5/Al of different component content respectively mainly according to the difference of production purpose
2O
3/ kaolin, Y/AlAl
2O
3/ kaolin or USY/Al
2O
3Three kinds of catalyzer of/kaolin, and on the circulating fluid bed catalysis cracking unit of forming by riser reactor-revivifier processing treatment animal and vegetable oil or rubbish oil, thereby produce or on purpose voluminous gasoline and diesel oil, propylene and liquefied gas.
CN200610089354.3 discloses and has a kind ofly utilized animal grease or/and the method for Vegetable oil lipoprotein system alkene, with Vegetable oil lipoprotein and/or animal grease is raw material, press raw material: the weight ratio of solid acid catalyst=1: 1-28, under 400-700 ℃, carry out catalytic pyrolysis, preparation ethene, propylene and butylene, acidic molecular sieve in the described catalyzer: kaolin or illiteracy holder soil: silicon oxide or aluminum oxide=5-60%: 10-90%: 5-30%; Molecular sieve wherein is Y zeolite, ZSM-5 molecular sieve, beta molecular sieve, sapo molecular sieve analog or mordenite.Concrete catalyst for application is not provided among the embodiment of this application.
Summary of the invention
The technical problem to be solved in the present invention provides the method that a kind of biomass material is produced low-carbon alkene, and this method utilizes biomass material production low-carbon alkene to have higher productivity of low carbon olefin hydrocarbon.
The invention provides a kind of method of biomass material producing low-carbon alkene by catalytic pyrolysis, comprise biomass material or contain biomass contacting in riser tube or fluidized-bed reactor with the catalyzer that contains the five-ring supersiliceous zeolite, under the condition of catalytic pyrolysis, react with the raw material of hydrocarbon ils; Reaction product isolated and reclaimable catalyst; Reaction product is sent into subsequent separation system and is carried out product separation, obtains product liquid and the gaseous product that contains ethene, propylene, and reclaimable catalyst Returning reactor after stripping, regeneration recycles; Wherein said five-ring supersiliceous zeolite contains phosphorus and transition metal, described catalytic pyrolysis condition is: temperature of reaction 550-700 ℃, the weight ratio of catalyzer and oil fuel is 6-40, feeds diluent gas in the reaction process, and the weight ratio of diluent gas and raw material is 0.1-1: 1.
The present invention utilizes biomass material to produce the method for low-carbon alkene, uses phosphorous and pentasil zeolites transition metal, processing biological raw material under the condition of catalytic pyrolysis, and the productive rate of ethene is higher, has higher olefins yield than existing methods.For example, using the macroporous catalyst that contains 10 weight %ZRP zeolites, 10 weight %REHY zeolites, is raw material with the long residuum of 10 weight % and the oleic acid of 90 weight %, at 640 ℃ of temperature of reaction, agent-oil ratio 20, air speed 10h
-1, water injection rate (accounting for raw material) 50 weight % react, and the productive rate of low-carbon alkene is 43.04 weight %, and ethylene yield is 10.25 weight %, and productivity of propylene is 20.54 weight %, the butylene productive rate is 12.26 weight %; And use contains the catalyzer of 10%HZSM-5 zeolite, 10 weight %REHY zeolites, react according to the method described above, the productive rate of low-carbon alkene is 38.64 weight %, and yield of ethene is 9 weight %, propene yield is 18.76 weight %, and the butylene productive rate is 10.88 weight %.
Embodiment
In the catalytic cracking method provided by the present invention, the anhydrous chemical expression of the five-ring supersiliceous zeolite of described phosphorous and transition metal is counted (0-0.3) Na with the quality of oxide compound
2O (0.3-5) Al
2O
3(1-10) P
2O
5(0.7-20) M
xO
y(70-98) SiO
2, wherein element M is selected from one or more among RE, Fe, Co, Ni, Cu, Zn, Mo and the Mn, and RE is a rare earth element, and x represents the atomicity of M, and y represents the atomicity of O.The anhydrous chemical expression of the five-ring supersiliceous zeolite of described phosphorous and transition metal is preferably (0-0.2) Na in the quality of oxide compound
2O (0.9-5) Al
2O
3(1.5-7) P
2O
5(1.4-15) M
xO
y(82-92) SiO
2, x represents the atomicity of M, and y represents the atomicity of O, and M is a kind of among RE, Fe, Co or the Ni.Described five-ring supersiliceous zeolite is for example: ZSM-5, ZSM-8, ZSM-11 are preferably the ZSM-5 zeolite.Described five-ring supersiliceous zeolite phosphorous and transition metal can be according to disclosed method preparation among existing method preparation example such as the Chinese patent CN1465527A.
In the catalytic cracking method provided by the present invention, described catalyzer also can contain the molecular sieve of other type, for example one or more in y-type zeolite, the β zeolite; Described y-type zeolite is preferably one or more in the HY zeolite of the overstable gamma zeolite, HY zeolite of the y-type zeolite, overstable gamma zeolite of phosphorous and/or rare earth, phosphorous and/or rare earth, phosphorous and/or rare earth, one or more among more preferably super steady Y, REY or the REHY.
In the catalytic cracking method provided by the invention, described catalyzer is preferably macroporous catalyst; Described macroporous catalyst comprises the five-ring supersiliceous zeolite of phosphorous and transition metal and comprises the carrier of aluminum oxide, the pore volume that is no more than the hole of 100nm with the aperture is a benchmark, the pore volume in the hole of described macroporous catalyst 6-20nm accounts for 20-80%, the pore volume that preferred described macroporous catalyst has the hole of following pore distribution:＜2nm accounts for 5-70%, the pore volume in the hole of 2-4nm accounts for 5-70%, the pore volume in the hole of 4-6nm accounts for 0-10%, the pore volume in the hole of 6-20nm accounts for 20-80%, and the pore volume in the hole of 20-100nm accounts for 0-40%.In the described macroporous catalyst＜pore volume in the hole of 2nm preferably accounts for 5-60%, more has choosing to account for 10-40%; The pore volume in the hole of 2-4nm preferably accounts for 10-60%, more preferably accounts for 10-50%, further preferably accounts for 15-40%; The pore volume in the hole of 6-20nm preferably accounts for 25-70%, more preferably 30-60%; The pore volume in the hole of 6-10nm accounts for 10-50% in the described catalyzer, preferably accounts for 15-40%.The hole of preferred 6-20nm is 0.5-8, more preferably 0.5-4 with the ratio of the pore volume in the hole of 2-4nm.Described macroporous catalyst is 0.19ml/g-0.4ml/g with the pore volume that nitrogen loading capacity method (BET method) records, and is preferably 0.196ml/g-0.30ml/g, more preferably 0.20-0.26ml/g.Nitrogen loading capacity method is measured the pore volume of catalyzer and is published the RIPP151-90 analytical procedure in " petrochemical complex analytical procedure " (RIPP experimental technique) that Yang Cuiding etc. write referring to Science Press 1990.Use macroporous catalyst can further improve the productive rate of low-carbon alkene, and have lower heavy oil productive rate.Alumina source self-alumina in the described carrier and in the precursor one or more thereof, the content of preferred described aluminum oxide is 5-80 weight %.Aluminum oxide and precursor thereof be aluminium colloidal sol, phosphorus aluminium colloidal sol, contain aluminium salt (for example various aluminates, the vitriol of aluminium, nitrate, halogenide), gama-alumina, η-aluminum oxide, θ-aluminum oxide, χ-aluminum oxide, have structure of similar to thin diaspore hydrated aluminum oxide, have a diaspore structure hydrated aluminum oxide, have the hydrated aluminum oxide of gibbsite structure and have in the hydrated aluminum oxide of bayerite structure one or more, excellent is pseudo-boehmite, or one or more the mixture in other precursor of pseudo-boehmite and aluminum oxide and aluminum oxide.
The carrier of described macroporous catalyst comprises aluminum oxide, also can comprise one or more of clay, the non-aluminium element oxide compound of IIIA and IVA family.Described non-aluminium element oxide source is from one or more of the oxide compound of described non-aluminium element or oxide compound precursor.For example, silicon oxide and precursor thereof can be selected from one or more in silicon sol, water glass, silicate, silicon-aluminum sol, silica-alumina gel and the various silicoorganic compound, are preferably water glass and/or silicon sol.Weight with carrier is benchmark, and the content of carrier medium clay soil and described non-aluminum oxide is no more than 95 weight %, and the content of preferably clay is no more than 60 weight %.In the method for preparing catalyst provided by the invention, described clay is to be customarily used in the clay of cracking catalyst one or more, for example one or more in kaolin, halloysite, polynite, diatomite, halloysite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite, the wilkinite.
Preferably also contain the metal component that is derived from IIA, IB, IIB, IVB family metal halide in the carrier of described macroporous catalyst, weight with carrier is benchmark, content in the described metal component of oxide compound is no more than 15 weight %, be preferably 0.1 weight %-12 weight %, more preferably 0.1 weight %-6 weight %.Described metal component is one or more in IV B and the II A family metal more preferably, further are preferably Ti and/or Mg.Contain described metal component in the carrier, the wear resisting property of catalyzer improves.
Described macroporous catalyst preferably contains the carrier of 60 weight %-95 weight %, the molecular sieve of 5 weight %-40 weight %; Contain the pentasil zeolites of the phosphorous and transition metal of 25 weight %-100 weight %, the y-type zeolite of 0-75 weight %, the β zeolite of 0-20 weight % in the described molecular sieve; The alumina content that is derived from aluminum oxide and/or aluminum oxide precursor in the described carrier is 5 weight %-100 weight %, and the content of other carrier component is no more than 95 weight %.
In the production low-carbon alkene method provided by the invention, the preparation method of described macroporous catalyst comprises the carrier of salic and/or its precursor, expanding agent and molecular sieve mixing, making beating, spray-dired step, wherein said expanding agent is selected from one or more in boric acid, an alkali metal salt, weight with carrier is benchmark, the weight ratio of described expanding agent and carrier is 0.1: 100-15: 100, be preferably 0.1: 100-10: 100.Described an alkali metal salt is preferably one or more in the soluble salt of basic metal K, Na or Li, for example one or more in borate, phosphoric acid salt, vitriol, nitrate, carbonate or the hydrochloride.Described carrier is mixed making beating with molecular sieve, know for those skilled in the art are described, the preparation slurries of carrier and molecular sieve can being pulled an oar respectively, and then two kinds of slurries are mixed; Also can in the preparation process of carrier, earlier the part carrier be mixed and making beating, introduce molecular sieve then, introduce other carrier and making beating again; Or introduce in the molecular sieve pulp carrier and making beating.Described expanding agent is introduced in the slurries before spraying drying.Preferred described expanding agent is introduced in the slurries of salic carrier.After described expanding agent was introduced, making beating disperseed expanding agent in slurries, preferred making beating at least 5 minutes, more preferably 10-90 minute.After introducing expanding agent, also aging to the slurries that contain expanding agent, described wearing out carried out under static state, and the aged temperature is preferably 50-80 ℃, and digestion time is 0.5-3 hour.
When macroporous catalyst of the present invention also contains II A, I B, II B, IV B family metal, also comprise the step of introducing II A, I B, II B, IV B family metal halide in the pulping process of its preparation.Described metal halide is preferably after introducing expanding agent, introduce before the spraying drying.
Among the macroporous catalyst preparation method of the present invention, described spraying drying is prior art, does not have particular requirement, and for example spray-dired exhaust temperature is 100 ℃-300 ℃.Described preparation method also can comprise roasting, washing and exsiccant step.The method of described roasting, drying and washing is a prior art, does not have particular requirement, and for example maturing temperature is 300 ℃-700 ℃, and the exsiccant temperature is 100 ℃-300 ℃; Be no more than 0.5 weight % with deionized water wash sodium oxide content to the catalyzer.
In the catalytic cracking method provided by the invention, described biomass are preferably one or more in the organic oxygen-containing compound that the long-chain carbon number is 10-24, described organic oxygen-containing compound is one or more in the compound of saturated, single unsaturated, polyunsaturated fatty acid and lipid acid, the compound of described lipid acid is carboxylic acid, ester and grease and class ester cpds, for example high-grade lipid acid, high-grade aliphatic ester, animal oil, vegetables oil, animal wax, vegetable wax, phosphoric acid ester; Saturated fatty acid content is 30-90% in the preferred described organic oxygen-containing compound (biomass), and monounsaturated fatty acids content is 2-60%, and polyunsaturated fatty acid is 8-68%.When saturated fatty acid content is high in the biomass material, help improving the productive rate of ethene in the product.
In the catalytic cracking method provided by the present invention, when use contains the raw material of biomass and hydrocarbon ils, be benchmark with the weight of raw material, the content of described hydrocarbon ils is no more than 99.9 weight %, the content of preferred described hydrocarbon ils is no more than 50 weight %, and more preferably the content of described hydrocarbon ils is 20-50 weight %.When the ratio of hydrocarbon ils in the raw material and biomass is 1: 4-1: in the time of 1, cracking stock has the relay effect, helps improving the productive rate of low-carbon alkene, especially the productive rate of ethene.Described hydrocarbon ils is preferably heavy oil.Described heavy oil is long residuum, vacuum residuum, vacuum gas oil, propane deasphalting oil for example.
In the catalytic cracking method provided by the invention, biomass are contacted with cracking catalyst react, temperature of reaction is preferably 600-650 ℃; The time of reaction is preferably 0.5-10 second, and more preferably 1-5 second, agent-oil ratio is preferably 10-30; The weight ratio of diluent gas and raw material is preferably 0.2-0.6: 1; The preferred 1.5-4 of reaction pressure * 10
5Handkerchief.For reducing the oil gas dividing potential drop, in reaction process, inject diluent gas, the weight ratio of diluent gas and raw material is 0.1-1: 1, be preferably 0.2-0.6: 1; Described diluent gas is water vapor or catalytic cracked dry gas.
Riser tube of the present invention, fluidized-bed reactor, reaction product isolated and reclaimable catalyst and product separation are well known to those skilled in the art, and the present invention does not have particular requirement.
The inventive method can be used for producing low-carbon alkene by biomass material.
Embodiment 1
Preparation of Catalyst: 20Kg decationized Y sieve water and 20.1Kg pseudo-boehmite (Shandong Aluminum Plant's Industrial products, solid content 63 weight %) are mixed, making beating, regulating its pH value with hydrochloric acid is 3; 72.6Kg decationized Y sieve water and 28.4Kg halloysite (Suzhou china clay company Industrial products, solid content 72.3 weight %) are mixed, pulled an oar 5 minutes, add potassium borate 2.0Kg (analytical pure) then, pulled an oar 15 minutes; Above-mentioned two kinds of slurries are mixed, stir, left standstill aging 1.5 hours at 65 ℃, keeping the pH value when aging is 2-4 (regulating with hydrochloric acid), cools the temperature to 55 ℃ then, and (the Qilu Petrochemical catalyst plant is produced, Al to add 13.0Kg aluminium colloidal sol
2O
3Content is 21.7 weight %), stirred 40 minutes, add molecular sieve pulp 33.0Kg and (wherein contain REHY zeolite 0.5kg, ZRP zeolite 11.0Kg; RE in the REHY zeolite
2O
3Content 8 weight %, silica alumina ratio is 7; Described ZRP zeolite by the ZSM-5 zeolite through phosphorus and transition metal modified obtaining, its silica alumina ratio (SiO
2/ Al
2O
3) be 40, phosphorus pentoxide content accounts for 3% of molecular sieve gross weight, Na
2O content is 0.1 weight %, RE
2O
3Content is 3 weight %, is catalyzer Shandong branch office of China Petrochemical Industry and produces), add TiCl again
42Kg stirs, spraying drying then, and the flush away Na ion that dissociates, drying obtains catalyst A.Catalyst pores distributes and sees Table 1, and the rerum natura of catalyzer sees Table 2.
Raw material: lard, saturated fatty acid content are 60 weight %, and monounsaturated fatty acids content is 30%, and polyunsaturated fatty acid is 10%.
Reaction evaluating: on the small fixed flowing bed device, react 640 ℃ of temperature of reaction.Catalyst sample is in advance through 800 ℃, 100% steam-treated 17 hours, loading amount 180 grams, agent-oil ratio 20, air speed 10h
-1, water injection rate (accounting for raw material) 50 weight %.Evaluation result sees Table 4.
Embodiment 2
Preparation of Catalyst: 20Kg decationized Y sieve water and 18.2Kg pseudo-boehmite (Shandong Aluminum Plant's Industrial products, solid content 63 weight %) are mixed making beating, and regulating its pH value with hydrochloric acid is 3; 72.6Kg decationized Y sieve water and 32.1Kg halloysite (Suzhou china clay company Industrial products, solid content 72.3 weight %) are mixed, pulled an oar 5 minutes, add vitriolate of tartar (technical grade, content 98 weight %) 5Kg then, pulled an oar 15 minutes.Above-mentioned two kinds of slurries are mixed, stir, left standstill aging 1.5 hours at 65 ℃, keeping the pH value is 3-4, cools the temperature to 55 ℃ again, adds 14Kg aluminium colloidal sol (Qilu Petrochemical catalyst plant product, Al
2O
3Content is 21.7 weight %), stirred 40 minutes, add molecular sieve pulp 25.0Kg and (contain REHY zeolite 2.5kg, ZRP zeolite 6.5Kg, 2.5 kilograms in β zeolite, the REHY zeolite is with embodiment 1, the ZRP zeolite be the ZSM-5 zeolite through phosphorus and transition metal modified obtaining, its silica alumina ratio (SiO
2/ Al
2O
3) be 80, phosphorus content accounts for 4% of molecular sieve gross weight, Na
2O content is 0.1 weight %, 4 weight %RE
2O
3), add TiCl again
45Kg stirs, and spray drying forming, the flush away Na ion that dissociates is drying to obtain catalyst sample B.Catalyst pores distribution transitivity sees Table 1, table 2.
Raw material: 50% grand celebration long residuum+50% lard (with embodiment 1 lard)
Reaction: on the small fixed flowing bed device, carry out reaction evaluating, 640 ℃ of temperature of reaction.Catalyst sample is in advance through 800 ℃, 100% steam-treated 17 hours, loading amount 180 grams, agent-oil ratio 20, air speed 10h
-1, water injection rate (accounting for raw material) 50%.Evaluation result sees Table 4.
Embodiment 3
Preparation of Catalyst: 20Kg decationized Y sieve water and 11.9Kg pseudo-boehmite (Shandong Aluminum Plant's Industrial products, solid content 63 weight %) are mixed making beating.72.6Kg decationized Y sieve water and 38.7Kg halloysite (Suzhou china clay company Industrial products, solid content 72.3 weight %) are mixed, pulled an oar 5 minutes, add 15.0Kg water glass (Qilu Petrochemical catalyst plant product, SiO then
2Content is 19.9 weight %), pulled an oar 15 minutes, with hydrochloric acid its pH value is transferred to 3.5 then, add vitriolate of tartar 3Kg, pulled an oar 15 minutes.Above-mentioned two kinds of slurries are mixed, stir, left standstill under 60-70 ℃ of temperature aging 1.5 hours, keeping the pH value is 2-4, cools the temperature to 55 ℃ then, adds 13.5Kg aluminium colloidal sol (Qilu Petrochemical catalyst plant product, Al
2O
3Content is 21.7 weight %), stirred 40 minutes, add molecular sieve pulp 32.1Kg (wherein contain REHY zeolite 0.5Kg, ZRP zeolite 8.5Kg, β zeolite 0.5Kg, ZRP zeolite be the ZSM-5 zeolite through phosphorus and transition metal modified obtaining, its silica alumina ratio (SiO
2/ Al
2O
3) be 40, phosphorus content accounts for 3% of molecular sieve gross weight, Na
2O content is 0.1 weight %, 3 weight %RE
2O
3)), add TiCl again
45Kg stirs, and spray drying forming, the flush away Na ion that dissociates is drying to obtain catalyst sample C.Catalyst pores distribution transitivity sees Table 1, table 2.
Raw material: 75 weight % grand celebration long residuums+25 weight % plam oils (saturated fatty acid content is 50 weight %, and monounsaturated fatty acids content is 33 weight %, and polyunsaturated fatty acid is 17 weight %).
Reaction: on the small fixed flowing bed device, carry out reaction evaluating, 640 ℃ of temperature of reaction.Catalyst sample is in advance through 800 ℃, 100% steam-treated 17 hours, and loading amount 180 grams, agent weight of oil are than 20, air speed 10h
-1, water injection rate (accounting for raw material) 50%.Evaluation result sees Table 4.
Embodiment 4
Preparation of Catalyst: 20Kg decationized Y sieve water and 11.9Kg pseudo-boehmite (Shandong Aluminum Plant's Industrial products, solid content 63 weight %) are mixed, and making beating transfers to 2.8 with hydrochloric acid with its pH value.72.6Kg decationized Y sieve water and 38.7Kg halloysite (Suzhou china clay company Industrial products, solid content 72.3 weight %) are mixed, and pulling an oar adds boric acid 1.75Kg (analytical pure) continuation making beating 15 minutes after 5 minutes.Above-mentioned two kinds of slurries are mixed, stir, left standstill aging 1.5 hours at 65 ℃, keeping the pH value is 2-4, cools the temperature to 60 ℃ then, adds 13.5Kg aluminium colloidal sol (Qilu Petrochemical catalyst plant product, Al
2O
3Content is 21.7 weight %), stirred 40 minutes, add molecular sieve pulp 32.1Kg (wherein contain REHY zeolite 5.0kg, ZRP zeolite 5.0Kg, REHY zeolite and ZRP zeolite are with embodiment 1), making beating adds TiCl again
40.5Kg, stirring, spray drying forming, the flush away Na ion that dissociates is drying to obtain catalyst sample D.Catalyst pores distribution transitivity sees Table 1, table 2.
Raw material: 10% grand celebration long residuum+90% oleic acid (cis-9-18 (carbon) olefin(e) acid).
Processing condition: on the small fixed flowing bed device, carry out reaction evaluating, 640 ℃ of temperature of reaction.Catalyst sample is in advance through 800 ℃, 100% steam-treated 17 hours, loading amount 180 grams, agent-oil ratio 20, air speed 10h
-1, water injection rate (accounting for raw material) 50%.Evaluation result sees Table 5.
Embodiment 5
Catalyzer: 20Kg decationized Y sieve water and 11.9Kg pseudo-boehmite (Shandong Aluminum Plant's Industrial products, solid content 63 weight %) are mixed, and making beating transfers to 3 with hydrochloric acid with its pH value.72.6Kg decationized Y sieve water and 38.7Kg halloysite (Suzhou china clay company Industrial products, solid content 72.3 weight %) are mixed making beating.Above-mentioned two kinds of slurries are mixed, stir, left standstill aging 1.5 hours at 65 ℃, keeping the pH value is 2-4, cools the temperature to 60 ℃ then, adds 13.5Kg aluminium colloidal sol (Qilu Petrochemical catalyst plant product, Al
2O
3Content is 21.7 weight %), stirred 40 minutes, add molecular sieve pulp 32.1Kg (wherein containing REHY zeolite 5.0kg, ZRP zeolite 5.0Kg) with the zeolite of embodiment 1, making beating, spray drying forming, the flush away Na ion that dissociates is drying to obtain catalyst sample E.Catalyst pores distribution transitivity sees Table 1, table 2.
Raw material is raw materials used identical with embodiment 4.
Processing condition: on the small fixed flowing bed device, carry out reaction evaluating, 640 ℃ of temperature of reaction.Catalyst sample is in advance through 800 ℃, 100% steam-treated 17 hours, loading amount 180 grams, agent-oil ratio 20, air speed 10h
-1, water injection rate (accounting for raw material) 50%.Evaluation result sees Table 5.
Comparative Examples 1
Catalyzer: be the catalyst B of embodiment 2.
Raw material: 100% grand celebration long residuum.
Processing condition: on the small fixed flowing bed device, react 640 ℃ of temperature of reaction.Catalyst sample is in advance through 800 ℃, 100% steam-treated 17 hours, loading amount 180 grams, agent-oil ratio 20, air speed 10h
-1, water injection rate (accounting for raw material) 50%.Evaluation result sees Table 4.
Comparative Examples 2
Method according to embodiment 5 prepares catalyzer, and different is to use the HZSM-5 of equivalent to replace the ZRP molecular sieve, obtains catalyzer DB2.
Method according to embodiment 5 is that catalyzer carries out catalytic cracking reaction with DB2, and it the results are shown in Table 5.
Comparative Examples 3
Method according to embodiment 5 prepares catalyzer, and different is with 10Kg HZSM-5 replacement 5Kg Y zeolite and 5Kg ZRP zeolite wherein, gets catalyzer DB3, and the condition according to embodiment 3 is that catalyzer reacts with DB3 then, the results are shown in Table 4.
Table 1
Table 2
| Embodiment | ??1 | ??2 | ??3 | ??4 | ??5 |
| Catalyzer | ??A | ??B | ??C | ??D | ??E |
| ??AI，％ | ??1.1 | ??1.3 | ??1.9 | ??1.6 | ??2.0 |
| ??V BET，ml/g | ??0.218 | ??0.281 | ??0.247 | ??0.240 | ??0.189 |
Table 3
| Stock oil | The grand celebration long residuum |
| Density (20 ℃), g/cm 3Carbon residue, m% hydrogen richness, m% sulphur content, m% metal content, ppm Fe Ni V Na | ??0.8938??4.6??12.89??0.13??4.9??4.3??0.2??5.2 |
Table 4
Table 5
Embodiment 6
Method according to embodiment 2 prepares catalyzer, and different is, and (silica alumina ratio 31 contains P with the ZSP zeolite of equivalent
2O
56 weight % contain Fe
2O
32 weight %) replacement ZRP zeolite wherein obtains catalyzer F.With the mixture material that contains 25 weight % grand celebration long residuums and 75% peanut oil then according to the reaction conditions of embodiment 2, under 600 ℃, catalyzer F is carried out reaction evaluating, its ethylene yield is 10.98 weight %, and productivity of propylene is 22.67 weight %, and fourth hydrocarbon productive rate is 11.34 weight %.
Embodiment 7
Method according to embodiment 4 prepares catalyzer, and different is, 7.5Kg is phosphorous with comprising for molecular sieve pulp wherein, (silica alumina ratio is 60 to the ZSM-5 zeolite of rare earth and nickel, P
2O
5Content 3 weight %, RE
2O
3Content 3.5 weight %, nickel oxide content 5 weight %), the molecular sieve pulp of 10KgDASY0.0 zeolite (catalyzer Shandong branch office of China Petrochemical Industry product) replaces, kaolinic add-on is 28.3Kg, obtains catalyzer G.
Reaction conditions according to embodiment 2, (saturated fatty acid content is 40 weight % with 35 weight % grand celebration long residuums and 65 weight % mixing animal oil, monounsaturated fatty acids content is 20 weight %, polyunsaturated fatty acid is 40 weight %) mixing oil formed is raw material, carry out reaction evaluating on the small fixed flowing bed device, productivity of low carbon olefin hydrocarbon is 49.21 weight %.
Embodiment 8
20Kg decationized Y sieve water and 9.9Kg pseudo-boehmite (Shandong Aluminum Plant's Industrial products, solid content 63m%) are mixed, making beating, regulating its pH value with hydrochloric acid is 3; 72.6Kg decationized Y sieve water and 38.7Kg halloysite (Suzhou china clay company Industrial products, solid content 72.3 weight %) are mixed, pulled an oar 5 minutes, add potassium borate 4.01Kg (analytical pure) then, pulled an oar 15 minutes; Above-mentioned two kinds of slurries are mixed, stir, left standstill aging 1.5 hours at 65 ℃, keeping the pH value is 2-4 (regulating with hydrochloric acid), cools the temperature to 55 ℃ then, and (the Qilu Petrochemical catalyst plant is produced, Al to add 13.5Kg aluminium colloidal sol
2O
3Content is 21.7 weight %), stirred 40 minutes, adding molecular sieve pulp 18.7Kg (wherein contain REHY zeolite 1.0kg, ZRP zeolite 5.2Kg, used zeolite is with embodiment 1), add TiCl again
44Kg stirs, spraying drying then, and the flush away Na ion that dissociates, drying obtains catalyzer F.Its pore distribution sees Table 1.The mixing oil of forming with 50 weight % butter and 50 weight % Trisun Oil R 80s is a raw material, reacts at 620 ℃ according to the condition of embodiment 2, and its productivity of low carbon olefin hydrocarbon is 43.5 weight %.
Claims (15)
1. the method for a producing low-carbon alkene by catalytic pyrolysis of biomass, comprise biomass material or contain biomass contacting in riser tube or fluidized-bed reactor with the catalyzer that contains the five-ring supersiliceous zeolite, under the condition of catalytic pyrolysis, react with the raw material of hydrocarbon ils; Reaction product isolated and reclaimable catalyst; Reaction product is sent into subsequent separation system and is carried out product separation, obtains product liquid and the gaseous product that contains ethene, propylene, and reclaimable catalyst Returning reactor after stripping, regeneration recycles; Wherein said five-ring supersiliceous zeolite contains phosphorus and transition metal, described catalytic pyrolysis condition is: temperature of reaction 550-700 ℃, the weight ratio of catalyzer and stock oil is 6-40, feeds diluent gas in the reaction process, and the weight ratio of diluent gas and raw material is 0.1-1: 1.
2. method according to claim 1 is characterized in that, the anhydrous chemical expression of the five-ring supersiliceous zeolite of described phosphorous and transition metal is counted (0-0.3) Na with the quality of oxide compound
2O (0.3-5) Al
2O
3(1-10) P
2O
5(0.7-20) M
xO
y(70-98) SiO
2, wherein element M is selected from one or more among RE, Fe, Co, Ni, Cu, Zn, Mo and the Mn, and RE is a rare earth element, and x is the valency of oxygen, and y is the valency of transition metal.
3. method according to claim 1 is characterized in that described catalyzer also contains the carrier that comprises aluminum oxide, and the pore volume that is no more than the hole of 100nm with the aperture is a benchmark, and described catalyzer has following pore distribution; The pore volume in the hole of＜2nm accounts for 5-70%, and the pore volume in the hole of 2-4nm accounts for 5-70%, and the pore volume in the hole of 4-6nm accounts for 0-10%, and the pore volume in the hole of 6-20nm accounts for 20-80%, and the pore volume in the hole of 20-100nm accounts for 0-40%.
4. method according to claim 3 is characterized in that, described catalyzer is prepared by the method that comprises the steps: carrier, zeolite and the expanding agent that will comprise aluminum oxide and/or aluminum oxide precursor mix, making beating, spraying drying; Described expanding agent is selected from one or more in boric acid, an alkali metal salt, is benchmark with the weight of carrier, and the weight ratio of described expanding agent and carrier is 0.1: 100-15: 100.
5. according to claim 3 or 4 described methods, it is characterized in that the hole of 6-20nm is 0.5 with the ratio of the pore volume in the hole of 2-4nm in the described catalyzer: 1-8: 1.
6. according to claim 3 or 4 described methods, it is characterized in that the pore volume in the hole of 6-20nm accounts for 25-70% in the described catalyzer.
7. according to claim 3 or 4 described methods, it is characterized in that the pore volume in the hole of 6-10nm accounts for 10-50% in the described catalyzer.
8. according to claim 3 or 4 described methods, it is characterized in that the pore volume in the hole of 2-4nm accounts for 10-60% in the described catalyzer, the pore volume in the hole of＜2nm accounts for 5-60%.
9. according to claim 3 or 4 described methods, it is characterized in that the pore volume that described catalyzer records with the BET method is 0.19ml/g-0.4ml/g.
10. method according to claim 4, it is characterized in that, described aluminum oxide and/or aluminum oxide precursor be pseudo-boehmite or pseudo-boehmite and be selected from aluminium colloidal sol, phosphorus aluminium colloidal sol, contain aluminate, have a diaspore structure hydrated aluminum oxide, have the hydrated aluminum oxide of gibbsite structure and have one or more mixture in the hydrated aluminum oxide of bayerite structure; Described supersiliceous zeolite is one or more among ZSM-5, ZSM-8, the ZSM-11.
11. according to claim 3 or 4 described methods, it is characterized in that, described catalyzer contains the carrier of 60 weight %-95 weight %, the molecular sieve of 5 weight %-40 weight %, contain five-ring supersiliceous zeolite, 0-75 weight %Y type zeolite, the 0-20 weight % β zeolite of the phosphorous and transition metal of 25 weight %-100 weight % in the described molecular sieve, the content of aluminum oxide is 5-100 weight % in the carrier.
12. method according to claim 1 is characterized in that, described biomass are one or more in the compound of the lipid acid of 10-24 and lipid acid for the long-chain carbon number.
13. method according to claim 12 is characterized in that, the compound of described lipid acid is one or more in ester, grease and the class ester; Saturated fatty acid content is 30-90 weight % in the described biomass, and monounsaturated fatty acids content is 2-60 weight %, and polyunsaturated fatty acid is 8-68 weight %.
14. method according to claim 1 is characterized in that, contains biomass and heavy oil in the described raw material, the content of described heavy oil is 20-50 weight %.
15. method according to claim 1 is characterized in that, described temperature of reaction is 600-650 ℃, and agent-oil ratio is 10-30, and the weight ratio of diluent gas and raw material is 0.2-0.6: 1; The time of reaction is 0.5-10 second, and reaction pressure is 1.5-4 * 10
5Handkerchief.
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