[go: up one dir, main page]

WO2009092282A1 - 含酸劣质原油转化催化剂及其制备方法和应用 - Google Patents

含酸劣质原油转化催化剂及其制备方法和应用 Download PDF

Info

Publication number
WO2009092282A1
WO2009092282A1 PCT/CN2009/000032 CN2009000032W WO2009092282A1 WO 2009092282 A1 WO2009092282 A1 WO 2009092282A1 CN 2009000032 W CN2009000032 W CN 2009000032W WO 2009092282 A1 WO2009092282 A1 WO 2009092282A1
Authority
WO
WIPO (PCT)
Prior art keywords
catalyst
oil
molecular sieve
acid
mesoporous material
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/CN2009/000032
Other languages
English (en)
French (fr)
Inventor
Jun Long
Jiushun Zhang
Huiping Tian
Yuxia Zhu
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
Original Assignee
Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from CN2008100557931A external-priority patent/CN101480621B/zh
Priority claimed from CN200810112001XA external-priority patent/CN101586038B/zh
Application filed by Sinopec Research Institute of Petroleum Processing , China Petroleum and Chemical Corp filed Critical Sinopec Research Institute of Petroleum Processing
Priority to BRPI0907160-1A priority Critical patent/BRPI0907160B1/pt
Priority to JP2010541682A priority patent/JP5622588B2/ja
Priority to CA2711392A priority patent/CA2711392C/en
Priority to US12/812,148 priority patent/US8809216B2/en
Publication of WO2009092282A1 publication Critical patent/WO2009092282A1/zh
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • C10G45/12—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/7007—Zeolite Beta
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/80—Mixtures of different zeolites
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • C10G11/04—Oxides
    • C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/16—Clays or other mineral silicates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/42—Addition of matrix or binder particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/635—0.5-1.0 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/638—Pore volume more than 1.0 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0027—Powdering
    • B01J37/0045—Drying a slurry, e.g. spray drying

Definitions

  • the invention relates to a hydrocarbon oil conversion catalytic material and a preparation method thereof, and the application of the catalytic material in the pretreatment catalytic conversion process of acid-poor crude oil, more specifically, relating to a non-existent In the case of hydrogen, a catalytic material for catalytically converting an acid-poor crude oil and a preparation method thereof.
  • the acid-poor crude oil has a low hydrogen content, a high content of metals such as Ni and V, a high content of fused aromatic hydrocarbons, a high content of S and N, a high density, a large residual carbon value, and difficulty in cracking.
  • the catalytic cracking unit for processing such acid-containing inferior raw materials is forced to be a large amount of external slurry because the raw materials are difficult to be cracked, and as a result, the total yield of the liquid products (liquefied gas, gasoline, diesel) is decreased; due to the content of Ni and V Higher, the content of hydrogen in the product is greatly increased, and the catalyst is also strongly destructive.
  • a non-catalytic pretreatment method is to introduce the high residual carbon value and the high metal content of the feedstock oil into the demetallization and disability of the device similar to the fluid catalytic cracking.
  • the carbon zone in contact with the inert particles, at a temperature of at least 480 ° C and a contact time of less than 2 seconds, the coke and metal in the feedstock are deposited on the inert particles, and the particles are recycled into the charred zone to burn off the coke and burn off.
  • the inert particles of coke are recycled to the demetallization and carbon residue zones for re-contact with the acid-poor feedstock oil.
  • the feedstock oil treated by this method can be used as a raw material for FCC.
  • the acidic substances in crude oil refer to inorganic acids, phenols, mercaptans, fatty carboxylic acids and naphthenic acids. Naphthenic acid is the most important acidic oxide in crude oil, and its content accounts for about 90% of acidic oxides. Studies have shown that acid values in crude oil reaching 0.5 mg KOH / g cause significant corrosion to production and refining equipment, so the acid value of crude oil exceeding 0.5 mg KOH / g is called high acid crude oil.
  • naphthenic acid in petroleum can directly react with iron, causing corrosion of furnace tubes, heat exchangers and other refinery equipment; it can also react with protective film FeS on petroleum equipment to expose new metal equipment.
  • the surface is subject to new corrosion.
  • petroleum products such as gasoline, diesel, and kerosene quality indicators, there are usually acid values. Excessive acid values are likely to cause the same corrosion problems for end users.
  • Literature and patents describe methods for deacidification of crude oil, such as physical adsorption, heat treatment, thermal cracking, and catalytic hydrogenation, but these methods have not been put into practical use.
  • the physical adsorption method in the presence of an adsorbent, the acid-containing crude oil or fraction is subjected to heat treatment at a temperature of 250-350 ° C to adsorb and transfer the acid-containing compound in the crude oil, and the adsorbent may employ a spent catalytic cracking catalyst. Or heating a mixture of crude oil and alkaline earth metal oxide at 100-300 ° C to react an alkaline earth metal oxide with an organic acid or sulfide in the crude oil to form a precipitate of an alkaline earth metal carbonate and an alkaline earth metal sulfide, after separation A crude oil obtained by removing naphthenic acid and sulfide is obtained.
  • the catalytic hydrogenation method uses a Ni-Mo or Ni-Co hydrotreating catalyst with a carrier of alumina, and hydrotreats the acid-containing crude oil under a hydrogen partial pressure of 2-3 MPa and a reaction temperature of 250 ° C.
  • the decomposition of naphthenic acid into CO, C0 2 , H 2 0 and low molecular weight petroleum hydrocarbons can reduce the total acid value of crude oil from 2.6 mg KOH/g to 0.15 KOH/g.
  • Catalytic hydrogenation is a good deacidification effect, but it needs high pressure and high temperature resistant equipment, and hydrogen is required. The equipment investment is high and the process investment is large.
  • the high acid crude oil can be treated with Ni-Mo or Ni-Co hydrotreating catalyst at a temperature of 285-345 ° C, and the total acid value of the crude oil can be reduced from 4.0 mg KOH/g to 1.8 mg KOH. /g.
  • CN 1827744 A discloses a method for processing high acid value crude oil, which is to make the total after pretreatment
  • the crude oil having an acid value of more than 0.5 mgKOH/g is preheated and injected into the fluid catalytic cracking reactor to be contacted with the catalyst, and the reaction is carried out under catalytic cracking reaction conditions, and the naphthenic acid in the crude oil is cracked into hydrocarbons and co 2 , and separated.
  • the oil and gas and the catalyst are sent to the subsequent separation system, and the reacted catalyst is recycled after being stripped and regenerated.
  • the common practice of processing acid-poor crude oil is to mix with low-acid crude oil.
  • the acid value of the mixed crude oil is not more than 0.5 mgKOH/g, so the blending ratio of the acid-containing crude oil is limited.
  • the object of the present invention is to provide a catalyst for directly producing catalytically cracked crude oil containing acid and inferior crude oil, especially an acid value of more than 0.5 mg KOH/g, to produce a high value-added product, and a method for preparing the same. And a method of converting the crude oil using the catalyst.
  • the acid-poor crude oil conversion catalyst provided by the invention comprises, based on the total amount of the catalyst, the catalyst comprises 1-50 w% of mesoporous material, l-60 w% of molecular sieve, 5-98 w% of heat resistant inorganic oxide and 0- 70% clay.
  • the catalyst contains 5-40 w% of mesoporous material, 10-50 vv% of molecular sieve, 10-70 vv% of heat resistant inorganic oxide, 0-60% of clay based on the total amount of catalyst. More preferably, the catalyst contains 10-40 w% of mesoporous material and 20-40 w% of molecular sieve based on the total amount of catalyst.
  • the catalyst used in the present invention comprises a mesoporous material which is an amorphous material containing an alkaline earth metal oxide, silicon oxide and aluminum oxide.
  • the anhydrous chemical expression of the oxide is: (0- 0.3 ) Na 2 0- ( 1-50 ) ⁇ ⁇ ( 6-58 ) ⁇ 1 2 0 3 ⁇ ( 40-92 ) Si0 2 .
  • the anhydrous chemical expression of the mesoporous material is (0-0.2) Na 2 0- ( 2-30 ) ⁇ ⁇ ( 6-35 ) ⁇ 1 2 0 3 ' (by weight percent of the oxide) 60-92) Si0 2 .
  • M is selected from one or more of Mg, Ca and Ba, preferably Mg and/or Ca.
  • the mesoporous material has a specific surface area of 200-400 m 2 /g, a pore volume of 0.5-2.0 ml/g, preferably 1.0-2.0 ml/g; an average pore diameter of 8-20 nm, preferably 10-20 nm; The pore size is 5-15 nm, preferably 10-15 nm.
  • the mesoporous material in anhydrous form contains from 0.1 to 0.2% of Na 2 0, from 60 to 85% of SiO 2 and from 6 to 20% of A1 2 0 3 , based on the weight percent of the oxide.
  • the mesoporous material in anhydrous form contains 5-30% MO by weight percent of the oxide.
  • the molecules are screened from faujasite, Beta zeolite, molecular sieves having an MFI structure, and a mixture of one or more of the mordenite;
  • the heat resistant inorganic oxide is selected from the group consisting of a mixture of one or more of alumina, silica, and amorphous silica;
  • the clay is selected from the group consisting of kaolin, A mixture of one or more of kaolinite, montmorillonite, diatomaceous earth, halloysite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite, and bentonite.
  • the method for preparing the mesoporous material comprises: using an aluminum source, a silicon source and an alkaline earth solution at room temperature to
  • the aluminum source is selected from one or more of aluminum nitrate, aluminum sulfate, aluminum chloride and sodium metaaluminate; and the silicon source is selected from the group consisting of water glass.
  • the acid is selected from one or more of acid, hydrochloric acid and nitric acid; and the alkali is selected from the group consisting of ammonia water and hydroxide One or more of potassium and sodium hydroxide.
  • the amount of each component is such that the final catalyst contains, based on the total amount of the catalyst, from 1 to 50% by weight of the mesoporous material, l-60w 0 /.
  • Molecular sieve 5-98 w% of heat resistant inorganic oxide and 0-7 (1 ⁇ 2% clay.
  • the catalyst contains 5-40 w% of mesoporous material, 10-50 w% based on the total amount of catalyst Molecular sieve, 10-70 w% of heat resistant inorganic oxide, 0-60% by weight of clay. More preferably, the catalyst contains 10-4 (1 ⁇ 2% of mesoporous material and 20-4 based on the total amount of catalyst). (1 ⁇ 2% molecular sieve.
  • the catalyst provided by the present invention contains a mesoporous material containing an alkaline earth metal oxide, silicon oxide and aluminum oxide, the specific surface area is 200-400 m 2 /g, the pore volume is 0.5-2.0 ml/g, and the average pore diameter is 8. -20nm, wherein the presence of alkaline earth metal oxides is beneficial to promote the catalytic decomposition of organic acids in acid-poor crude oil, while high specific surface area, large pore volume and mesoporous pore size are beneficial to heavy metal chelate and colloid in acid-poor crude oil.
  • the entry and adsorption of molecules reduces the deactivation of the active center of the catalyst due to heavy metal deposition and coking.
  • the catalyst provided by the invention can directly catalytically crack the acid-containing inferior crude oil to produce a high value-added product, and at the same time react the acid value or acid of the product such as gasoline or diesel oil.
  • the degree meets the product requirements, and it is not necessary to refine the product due to high acid value or acidity.
  • the method for catalytically converting the acid-containing inferior crude oil comprises: pre-heating the raw material oil into the fluid catalytic cracking reactor after being preheated, contacting with the catalyst as described above, and performing the catalytic cracking reaction condition.
  • the reaction, the separated oil and gas and the catalyst to be produced are separated, and the reacted oil and gas is sent to a subsequent separation system, and the reacted catalyst is recycled after being stripped and regenerated; the composition of the catalyst and its content are as previously described.
  • the mesoporous material is an amorphous material containing an alkaline earth metal oxide, silicon oxide and aluminum oxide as described above, wherein the optional content of each component is as described above for the mesoporous material.
  • the catalyst provided by the method comprises a mesoporous material containing an alkaline earth metal oxide, silicon oxide and aluminum oxide, and has a specific surface area of 200-400 m 2 /g and a pore volume of 0.5-2.0 ml/g.
  • the pore diameter is 8-20nm, wherein the presence of alkaline earth metal oxide is beneficial to promote the catalytic decomposition of organic acid in acid-poor crude oil, and the high specific surface area, large pore volume and mesoporous pore size are favorable for heavy metal chelate in acid-poor crude oil.
  • the process provided by the present invention facilitates the direct catalytic cracking of acid-containing inferior crude oils to produce high value-added clean gasoline and low carbon olefin products.
  • the catalyst provided by the invention comprises a mesoporous material, a molecular sieve, a heat resistant inorganic oxide, with or without clay, based on the total amount of the catalyst, the mesoporous material content is l-50w%, and the molecular sieve content is l - 60 w%, the content of the heat resistant inorganic oxide is 5 to 98 w%, and the content of the clay is 0 to 70 w%.
  • the content of the mesoporous material is 5-40 w%
  • the content of the molecular sieve is 10-50 w%
  • the content of the heat resistant inorganic oxide is 10-70 w%
  • the content of the clay is 0-60 w%.
  • the catalyst contains 10-40 > v% mesoporous material and 20-40 w% molecular sieve based on the total amount of catalyst.
  • the mesoporous material is an amorphous material containing an alkaline earth metal oxide, silicon oxide and aluminum oxide, and the anhydrous chemical expression is: (0-0.3) Na 2 CK 1-50. ⁇ ( 6-58 ) ⁇ 1 2 0 3 ⁇ ( 40-92 ) Si ⁇ 2 , preferably, the anhydrous chemical expression is: ( 0-0.2 ) Na 2 0- ( 2-30 ) ⁇ ( 6-35 ) ⁇ 1 2 0 3 ⁇ ( 60-92 ) Si0 2 .
  • the mesoporous material in anhydrous form contains 0.1-0.2% Na 2 0, 60-85 % Si ⁇ 2 and 6-20% A1 2 0 3 in weight percent of the oxide.
  • the mesoporous material in anhydrous form contains 5-30% MO by weight percent of the oxide.
  • the alkaline earth metal M is selected from one or more of Mg, Ca and Ba, preferably Mg and/or
  • the molecule is selected from a mixture of one or more of macroporous and mesoporous molecular sieves which are commonly used as active components of cracking catalysts, such as faujasite, beta zeolite, molecular sieves having an MFI structure. And a mixture of one or more of mordenite.
  • the faujasite described therein is a mixture of one or more of HY, REY, REHY, USY, REUSY, DASY, DOSY and REDASY.
  • the rare earth content (in terms of RE 2 0 3 ) of REY, REHY, REUSY, REDASY, DOSY is 0 ⁇ 5-20 ⁇ %.
  • the faujasite described therein may also be modified by one or more elements such as Ba, Ca, Fe, Mg, P, Sr, Sn, Sb, Ti, Zn, Zr, etc.
  • the rare earth content (in terms of RE 2 0 3 ) of REY, REHY, REUSY, REDASY, DOSY is 0.5-20 w%.
  • the molecular sieve of the MFI structure mentioned therein is a mixture of one or more of ZSM-5 and ZRP series molecular sieves.
  • the molecular sieve of the MFI structure may also be RE, P, Fe, Co, Ni, Cu,
  • ZSM-5 and ZRP series molecular sieves modified with one or more elements such as Zn, Mo, Mn, Ga, Sn, and the like.
  • the Beta zeolite may also be a Beta zeolite modified with one or more elements such as RE, P, Fe, Co, Ni, Cu, Mn, Zn and Sn.
  • the heat resistant inorganic oxide is selected from one or more of a heat resistant inorganic oxide used as a cracking catalyst substrate and a binder component, such as alumina, silica and none.
  • a binder component such as alumina, silica and none.
  • One or more of the shaped silicon aluminum are well known to those skilled in the art.
  • the clay is selected from the group consisting of one or a mixture of clays used as an active component of a cracking catalyst, such as kaolin, halloysite, montmorillonite, diatomaceous earth, halloysite, saponite, and rector a mixture of one or more of sepiolite, attapulgite, hydrotalcite and bentonite. Among them, a mixture of one or more of kaolin, halloysite and montmorillonite is preferred. These clays are well known to those skilled in the art.
  • the preparation method of the catalyst provided by the invention may be added or partially added to the heat-resistant inorganic oxide and/or its precursor before aging. In order to make the catalyst have better wear resistance, it is preferred to add before the aging. Part of the heat-resistant inorganic oxide and/or its precursor, after aging, the remaining heat-resistant inorganic oxide and/or its precursor, the first added portion and the later added portion
  • the weight ratio of the heat-resistant inorganic oxide added first in the catalyst to the heat-resistant inorganic oxide added later is 1: (0.1 -10), preferably 1: (0.1-5).
  • the clay may be added before or after aging, and the order in which the clay is added has no effect on the performance of the catalyst.
  • an acid is added to make the pH of the slurry 1-5, and the temperature is aged at 30-90 ° C. 10 hours.
  • the acid is selected from one or more of a water-soluble inorganic acid and an organic acid, preferably one or more of hydrochloric acid, nitric acid, phosphoric acid and a carboxylic acid having 1 to 10 carbon atoms. mixture.
  • the acid is used in an amount such that the pH of the slurry is 1-5, preferably 1.5-4.
  • the aging temperature is 30-90 ° C, preferably 40-80 Torr, and the aging time is 0.1-10 hours, preferably 0.5-8 hours.
  • the precursor of the heat resistant inorganic oxide refers to one or more of substances capable of forming the heat resistant inorganic oxide during the preparation of the catalyst.
  • the precursor of the alumina may be selected from the group consisting of hydrated alumina and/or aluminum sol; the hydrated alumina is selected from the group consisting of boehmite (boehmite) and pseudo-boehmite (pseudo-boehmite).
  • boehmite boehmite
  • pseudo-boehmite pseudo-boehmite
  • the precursor of silicon oxide may be selected from one or more of silica sol, silicone gel and water glass.
  • the precursor of the amorphous silicon aluminum may be selected from the group consisting of a silica alumina sol, a mixture of a silica sol and an aluminum sol, and one or more of a silica-alumina gel. Precursors of these heat resistant inorganic oxides are well known to those skilled in the art.
  • the amount of each component is such that the final catalyst contains, based on the total amount of the catalyst, 1-50 vv% of the mesoporous material, l-60 w% of the molecular sieve, 5-98>v% Heat resistant inorganic oxide and 0-70 /. Clay.
  • the amount of each component is such that the final catalyst contains, based on the total amount of the catalyst, 5-40 w% of the mesoporous material, 10-50 w% of the molecular sieve, 10-70 w% of the heat resistant inorganic oxide, 0 -60%% clay. More preferably, the catalyst contains 10-40 w% of mesoporous material and 20-40 w% of molecular sieve based on the total amount of catalyst.
  • the drying method and conditions of the slurry are well known to those skilled in the art.
  • the drying method may be air drying, drying, blast drying or spray drying, preferably spray drying.
  • the drying temperature may be from room temperature to 400 ° C, preferably from 100 to 350 ° C.
  • the solid content of the slurry before drying is preferably from 10 to 50% by weight, more preferably from 20 to 50% by weight.
  • the calcination conditions after the slurry is dried are also known to those skilled in the art.
  • the calcination temperature after drying of the slurry is 400-700 ° C, preferably 450-65 CTC, and the calcination time is It is preferably 0.5 hours, preferably 0.5 to 100 hours, more preferably 0.5 to 10 hours.
  • the preparation method of the mesoporous material comprises neutralizing the aluminum source, the silicon source and the alkaline earth solution at room temperature to 85 ° C, and adjusting the gelation end point pH by acid or alkali. 7-9, aging at room temperature to 90 ° C for 1-10 hours, the obtained solid precipitate is subjected to ammonium exchange to remove impurity ions to obtain an ammonium exchanged gel, which may be further dried and calcined.
  • the aluminum source used is selected from the group consisting of aluminum nitrate, aluminum sulfate, aluminum chloride and sodium metaaluminate; or the mixture of silicon sources selected from the group consisting of water glass, sodium silicate, tetraethyl a mixture of one or more of silicon and silicon oxide;
  • the acid used is selected from the group consisting of a mixture of one or more of sulphuric acid, hydrochloric acid and nitric acid;
  • the base used is selected from the group consisting of ammonia, potassium hydroxide and hydrogen. a mixture of one or more of sodium oxide.
  • the ammonium salt used for the exchange is selected from any one of ammonium chloride, ammonium nitrate, ammonium carbonate and ammonium hydrogencarbonate.
  • the mesoporous material may be added in the form of a gel during the preparation of the catalyst, or may be added as a solid after drying or calcination, the form of addition of the mesoporous material having no effect on the performance of the catalyst.
  • a catalytic conversion catalyst as described above is used, the method comprising the steps of:
  • the pre-treated feedstock oil is preheated and injected into the catalytic cracking reactor, contacted with the catalyst, and reacted under catalytic cracking reaction conditions to separate the reacted oil and gas and the catalyst to be produced, and the reacted oil and gas is sent to the subsequent Separation system, the reacted catalyst is recycled after being stripped and regenerated
  • the catalytic cracking reaction condition is: the reaction temperature is 450-650
  • the catalytic cracking reaction condition is: the reaction temperature is 480-60 CTC, the absolute pressure in the reaction zone is 0.1-0.5 MPa, the space velocity is 10-20, and the weight ratio of the catalyst to the feedstock oil is 3-15.
  • a preferred solution is to preheat the pretreated feedstock oil to
  • the high-acid crude oil is partially subjected to an electric desalination process to partially remove a metal having a poisoning effect on the catalytic cracking catalyst contained in the high-acid crude oil and water having an adverse effect on the operation of the catalytic cracking device.
  • the desalted crude oil After the desalted crude oil is heated, it enters the catalytic cracking reactor and is brought into contact with the regenerated catalyst and reacted.
  • the electroless desalination of the crude oil is a process well known to those skilled in the art.
  • the general operation method is that the water which meets the requirements of electric desalination is mixed with the demulsifier and/or the demetallizing agent, and then heated, and then mixed with the high-acid crude oil after the temperature rise, and the mixed stream enters the first-stage desalting tank for electric desalination to separate the water.
  • the oil, the separated oil is mixed with the water containing the demulsifier and/or the demetallizing agent and heated by the heat exchanger, and then enters the secondary desalting tank.
  • the acid value of the raw material oil is more than 0.5 mgKOH/g, wherein the sum of the contents of the heavy metal nickel and vanadium is more than 10 ppm, the sulfur content is more than 1000 ppm, and the residual carbon value is higher than 3 w%.
  • the characteristic factor K value is a function of the average boiling point and relative density of the oil.
  • paraffin-based crude oil In acid-containing crude oil, paraffin-based crude oil generally contains more than 50% of alkanes, which is characterized by lower density, higher wax content, less sulfur and colloid, and characteristic factor ⁇ value greater than 12.0; It is characterized by more naphthenes and aromatic hydrocarbons, low freezing point, generally containing sulfur, colloidal and asphaltenes, and characteristic factor ⁇ value less than 11.5; the nature of intermediate-based crude oil is between these two types, characteristic factor The ⁇ value is 11.5-12.0.
  • the preferred two treatment methods are: for crude oil with total acid value greater than 0.5 mg OH/g and characteristic factor K value less than 12.5, the pretreated crude oil is preheated and introduced into the catalytic cracking reaction system.
  • the pretreated crude oil is directly introduced into the catalytic cracking reactor after contact with the catalyst, and reacted under catalytic cracking reaction conditions. Separating the reacted oil and gas and the catalyst to be produced, reacting oil and gas The product is sent to a subsequent separation system to obtain products of different distillation ranges; the catalyst to be produced is recycled after being stripped and regenerated; the molecular sieve in the catalyst is a Y-type molecular sieve, a molecular sieve having an MFI structure, and an optional ⁇ molecular sieve.
  • the content of the cerium type molecular sieve is 10 to S0 wt%
  • the molecular sieve content of the MFI structure is 10 to 90 wi%
  • the content of the ⁇ molecular sieve is 0 to 25 wi%.
  • the catalytic cracking reactor is selected from the group consisting of a fluidized bed reactor, a riser reactor, a downflow line reactor and a moving bed reactor.
  • the riser reactor is selected from one or more of an equal diameter riser reactor, a constant velocity riser reactor and a variable diameter riser reactor.
  • the fluidized bed reactor is selected from the group consisting of a fixed fluidized bed reactor, a bulk fluidized bed reactor, a bubbling bed reactor, a turbulent bed reactor, a fast bed reactor, a transport bed reactor, and a dense phase flow.
  • One or several of the chemical bed reactors are selected from the group consisting of a fluidized bed reactor, a riser reactor, a downflow line reactor and a moving bed reactor.
  • the riser reactor is selected from one or more of an equal diameter riser reactor, a constant velocity riser reactor and a variable diameter riser reactor.
  • the fluidized bed reactor is selected from the group consisting of a fixed fluidized bed reactor, a bulk fluidized bed reactor, a
  • the catalyst and crude oil conversion method provided by the invention are suitable for directly producing high value-added products by directly catalytically cracking acid-containing inferior crude oil or liquid fraction thereof with an acid value of crude oil greater than 0.5 mg KOH/g and a residual carbon value of more than 3 w%, and a reaction product such as gasoline.
  • the acid value or acidity of diesel oil meets the product requirements, and it is not necessary to refine the product due to high acid value or acidity.
  • the catalyst provided by the invention can also be directly Processing, and has better economic benefits.
  • the acid value, residual carbon and heavy metal content of the acid-poor crude oil can be effectively reduced, and the quality of the crude oil can be improved to be used as a raw material for catalytic cracking, which has better economic benefits.
  • Hydrochloric acid is produced by Beijing Chemical Plant, chemically pure, concentration 36-38w%;
  • Sodium water glass is commercially available, and the concentration of SiO 2 is 26.0 w%, and the modulus is 3.2;
  • the polyhydrate kaolin is produced by Suzhou Kaolin Company with a solid content of 74.0w%;
  • the pseudo-boehmite is an industrial product of Shandong Aluminum Factory with a solid content of 62.0 vv%;
  • the aluminum sol is a product of Qilu Catalyst Branch of Sinopec Corp., and the A1 2 0 3 content is 21.5w%;
  • DASY molecular sieve solid content: 92.0w ° /.
  • ZSP-2 molecular sieve solid content of 97.8w%
  • REHY molecular sieve solid content of 88.0w%)
  • Beta molecular sieve solid content of 95.2w%)
  • DOSY molecular sieve The solid content is 93.5w%), which are all produced by Sinopec Qilu Catalyst Branch.
  • Example 1 1750 g of a water glass solution having a concentration of 4 w% (by SiO 2 ) was placed in a beaker, and 350 g of a sodium metasilicate solution having a concentration of 4 w% (as A1 2 3 3 ), 150 g, was stirred under stirring.
  • An aluminum sulfate solution having a concentration of 4 w% (calculated as A1 2 3 3 ) and 250 g of a calcium chloride solution having a concentration of 4 w% (calculated as CaO) are simultaneously added to the above water glass solution, and the temperature is raised to 80 ° C for 4 hours;
  • the mesoporous material in the gel state is obtained by ammonium ion exchange, abbreviated as Nl.
  • N1 was dried at 120 Torr for 15 hours and calcined at 600 °C for 3 hours to obtain a mesoporous material, abbreviated as Gl.
  • the elemental analysis weight chemical composition of the sample is
  • This example illustrates a mesoporous material in a catalyst provided by the present invention and a process for its preparation.
  • Adding 125 g of a calcium chloride solution having a concentration of 4 w% (calculated as CaO) to 400 g of a 2.5 w% (as A1 2 3 3 ) aluminum sulfate solution, and adding the above mixed solution to a concentration of 1700 g under stirring 5 w% (in terms of Si0 2 ) in a water glass solution was heated to 80 ° C for 4 hours; ammonium ion exchange was carried out by the method of Example 1 to obtain a mesoporous material in a gel state, abbreviated as N2. Then, it was dried at 120 ° C for 15 hours and calcined at 600 ° C for 3 hours to obtain a mesoporous material, abbreviated as G2.
  • the elemental analysis weight chemical composition of the sample is
  • This example illustrates a mesoporous material in a catalyst provided by the present invention and a process for its preparation.
  • the elemental analysis weight composition of the sample was 0.1 Na 2 O 2 1.5 MgO 12.3 Al 2 O 3 '66.1 SiO 2 ; the specific surface parameters such as surface area and pore volume were listed in Table 1.
  • This example illustrates a mesoporous material in a catalyst provided by the present invention and a process for its preparation.
  • a 4w% (in terms of MgO) magnesium sulfate solution was placed in a beaker, and 1600 g of a 4 w% (as SiO 2 ) water glass solution was added to the above sulfuric acid solution under stirring, and then added.
  • the elemental analysis weight composition of the sample was 0.1Na 2 O29.8MgO.6.2Al 2 O 3 '63.9SiO 2 ; the specific surface parameters such as surface and pore volume are listed in Table 1.
  • This example illustrates the catalyst provided by the present invention and a process for the preparation thereof.
  • the slurry was spray-molded at a tail gas temperature of 250 ° C, washed, dried, and calcined.
  • the catalyst provided in the present invention having a composition of 20 w% mesoporous material, 35 w% DASY molecular sieve, 25 w% kaolin, 20 w% SiO 2 binder was obtained, abbreviated as Cl.
  • Comparative Example 1 A catalyst was prepared as in Example 7, except that no mesoporous material was added, and kaolinite was added. The amount of the catalyst was 6.1 kg, and a comparative catalyst having a composition of 35 w% DASY molecular sieve, 45% kaolin, and 20 vv% SiO 2 binder was obtained, abbreviated as CB 1.
  • This comparative example illustrates a comparative catalyst containing a V 2 0 5 mesoporous material and a process for its preparation.
  • the mesoporous material was prepared according to the method of Example 1. The difference was that vanadium oxalate was used instead of calcium chloride to obtain a vanadium-containing mesoporous material, which was abbreviated as GB1.
  • the elemental analysis weight chemical composition of the sample is
  • the catalyst was prepared according to the method of Example 7. The difference was that the vanadium-containing mesoporous material GB1 was used instead of G1 to obtain a composition of 20w% vanadium-containing mesoporous material, 35w% DASY molecular sieve, kaolin, 20w% SiO 2 binder. Catalyst, abbreviated as CB2.
  • This comparative example illustrates a comparative catalyst containing a Ti0 2 mesoporous material and a method for its preparation.
  • a mesoporous material was prepared according to the method of Example 1, except that titanium chloride was used instead of calcium chloride to obtain a mesoporous material containing titanium, which is abbreviated as GB2.
  • the elemental analysis weight composition of this sample was 0.2 Na 2 O'9.8TiO 2 19.8Al 2 O 3 '70.2SiO 2 .
  • the catalyst was prepared according to the method of Example 7. The difference was that the titanium-containing mesoporous material GB2 was used instead of G1 to obtain a 20 w% titanium-containing mesoporous material, 35 w% DASY molecular sieve, Z w% high cold soil, 20 w% SiO 2 .
  • a comparative catalyst for the binder abbreviated as CB3.
  • This example illustrates the catalyst provided by the present invention and a process for the preparation thereof.
  • the catalyst provided by the present invention having a composition of 30 w% mesoporous material, 18 w% DASY molecular sieve, 7 w% ZSP-2 molecular sieve, 201 ⁇ 4 % high alumina, 25 ⁇ % ⁇ 1 2 3 binder was obtained, abbreviated as C2.
  • Example 9 This example illustrates the catalyst provided by the present invention and a process for the preparation thereof.
  • Example 2 1.1 Kg of DAS Y molecular sieve, 2.1 KgZSP-2 molecular sieve was added to 6 Kg of decationized water, and after sufficient dispersion by a homogenizer, the molecular slurry was added to the above alumina-clay slurry, and then 1.5 kg (dry basis) was added to prepare in Example 2.
  • the gel state mesoporous material N2 was stirred for 0.5 h to obtain a catalyst slurry having a solid content of 21.2 vv%, and the obtained slurry was spray-dried at a temperature of 250 ° C, washed, dried, and calcined.
  • the catalyst provided by the present invention having a composition of 15 w% mesoporous material, 10 w% DASY molecular sieve, 20 w% ZSP-2 molecular sieve, 25 % kaolin, 30 v ⁇ % ⁇ 1 2 ⁇ 3 binder was obtained, abbreviated as C3.
  • This example illustrates the catalyst provided by the present invention and a process for the preparation thereof.
  • the catalyst of the present invention having a composition of 1 (1 ⁇ 2% mesoporous material, 20 w% REHY molecular sieve, 10 w% Beta molecular sieve, 30 w% kaolin, 30 w% Al 2 O 3 binder) was obtained, abbreviated as C4.
  • This example illustrates the catalyst provided by the present invention and a process for the preparation thereof.
  • Example 12 After adding 3.2 Kg of DOSY molecular sieve to 6.0 Kg of cationized water, and sufficiently dispersing through a homogenizer, 4.0 g of (dry basis) gel phase mesoporous material N3 prepared in Example 3 was added, and 14.0 kg of aluminum sol was uniformly stirred to obtain a solid content. For 17.8 vv% of the catalyst slurry, the resulting slurry was spray-dried at a temperature of 250 ° C, washed, dried, and calcined. The composition provided by the present invention was obtained as a 40 w% mesoporous material, 30 vv% DOSY molecular sieve, 30 w°/.
  • the catalyst for the Al 2 O 3 binder is abbreviated as C5.
  • This example illustrates the catalyst provided by the present invention and a process for the preparation thereof.
  • the catalyst provided in the present invention having a composition of 25 w% mesoporous material, 20 w% DASY molecular sieve, 301 ⁇ 4% kaolin, 25 v ⁇ % ⁇ 1 2 3 3 binder was obtained, abbreviated as C6.
  • This example illustrates the catalyst provided by the present invention and a process for the preparation thereof.
  • the catalyst was prepared as in Example 12, except that the mesoporous material prepared in Example 5 was used.
  • the present invention provides a composition obtained mesoporous material 25w%, 20w% DASY zeolite, 30w% high soil Yin, 25w% Al 2 0 3 catalyst binder, simply referred to as C7.
  • This example illustrates the catalyst provided by the present invention and a process for the preparation thereof.
  • the catalyst was prepared as in Example 12, except that the mesoporous material prepared in Example 6 was used.
  • G6 instead of G4, the catalyst of the composition of 25vv% mesoporous material, 20w% DASY molecular sieve, 30w% high alumina, 25 ⁇ % ⁇ 1 2 3 binder was obtained, which is abbreviated as C8.
  • the catalyst C 1 is subjected to metal contamination, and the amount of pollution is Fe: 6000 ppm, Ni: 9000 ppm,
  • Example 15 The method of Example 15 was used to contaminate, age and evaluate the catalytic performance of the catalyst, the difference being
  • the comparative catalysts CB1, CB2 and CB3 described in Comparative Examples 1-3 were respectively substituted for the catalyst C1 provided by the present invention.
  • the reaction conditions and results are shown in Table 3.
  • Catalysts C2 and C3 were aged for 17 hours under 100% steam.
  • the cracking performance of the catalyst was investigated using the acid-poor crude oil shown in Table 2.
  • the reaction conditions and product distribution are shown in Table 4.
  • the catalysts C4 and C5 were respectively contaminated with metal, and the amount of pollution was Fe: 8000 ppm, Ni:
  • the catalysts C6, C7, and C8 were respectively subjected to metal contamination, and the amount of contamination was Fe: 6000 ppm, Ni: 9000 ppm, Ca: 3000 ppm, and then the contaminated catalyst was aged under 100% steam for 8 hours.
  • the cracking performance of the catalyst was investigated by using the acid-poor crude oil 4 shown in Table 2.
  • the reaction temperature was 520 ° C, the weight ratio of the agent oil was 8, and the weight hourly space velocity was 16 hours -1 .
  • the reaction conditions and results are shown in Table 6.
  • the catalyst provided by the present invention can directly catalyze the acid-containing inferior crude oil having a higher acid content than 0.8 mg KOH/g, a colloid content greater than 16.6 w%, and a higher metal content.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Catalysts (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Description

含酸劣质原油转化催化剂及其制备方法和应用 技术领域
本发明是关于一种烃油转化催化材料及其制备方法，以及该催化材料 制成催化剂后在含酸劣质原油的预处理催化转化过程中的应用，更具体地 说， 是关于一种不存在氢的情况下， 将含酸劣质原油进行催化转化的催化 材料及其制备方法。 背景技术
随着世界对石油的需求量越来越大， 原油不断开采， 轻质原油资源逐 渐减少， 重质、 含酸劣质原油所占比例不断加大。 世界原油质量总的趋势 是变重， 变劣。 高硫含量、 高酸值、 高金属含量以及高残炭原油产量增长 很快。 据预测， 世界含酸劣质原油的产量将由现在的 16 %提高到 2010年 的 20 %。 在此背景下， 催化裂化装置加工含酸劣质油品原料是必须面对 的问题。
含酸劣质原油的氢含量低， Ni、 V等金属含量高，稠环芳烃的含量高， S、 N含量高， 密度大、 残炭值大、 难以裂解。 加工该类含酸劣质原料的 催化裂化装置， 由于原料难以裂解， 被迫大量外甩油浆， 其结果是液体产 品 (液化气、 汽油、 柴油)的总收率下降； 由于 Ni、 V的含量较高， 造成产 物中氢气的含量大大提高， 对催化剂也有较强的破坏作用， 为维持催化剂 的平衡活性， 势必要增加催化剂的单耗， 加注金属钝化剂也难以实现理想 的效果。 因此对于这类含酸劣质原油， 在进行加工之前最好能够进行改质 或转化处理， 提高原料的氢碳比， 减小金属含量和残炭值。
为了改善裂化原料油的性质、 降低残炭值和金属含量， 一种非催化 预处理方法是将高残炭值和高金属含量的原料油引入类似于流化催化裂 化的装置的脱金属和残炭区， 与惰性颗粒接触， 在至少 480°C和接触时间 少于 2秒的条件下， 原料油中的焦炭和金属沉积在惰性颗粒上， 这些颗粒 循环进入烧焦区烧去焦炭，烧掉焦炭的惰性颗粒重新循环进入脱金属和残 炭区， 与含酸劣质原料油再次接触。 经过该方法处理后的原料油可以作为 FCC的原料。
近年来， 含酸劣质原油的加工逐渐受到人们的重视， 国际市场上高酸 原油的数量也在不断增加， 2005 年， 世界高酸原油产量已经占原油总产 量的 5.5 %。 原油中酸性物质是指无机酸、 酚类、 硫醇、 脂肪羧酸和环烷 酸等， 环烷酸是原油中最主要的酸性氧化物， 其含量占酸性氧化物的 90 %左右。研究表明原油中的酸值达到 0.5mgKOH/g时就会对生产和炼制设 备造成显著腐蚀， 因此将原油中酸值超过 0.5mgKOH/g称为高酸原油。 在 石油加工过程中， 石油中的环烷酸可以直接与铁发生反应， 造成炉管、 换 热器及其它炼油设备腐蚀； 也可以与石油设备上的保护膜 FeS发生反应， 使金属设备露出新的表面， 受到新的腐蚀。 一般石油产品， 如汽油、 柴油、 煤油质量指标中通常也有酸值要求，过高的酸值容易给最终用户带来同样 的腐蚀问题。
文献和专利介绍原油脱酸的方法还有物理吸附法，热处理、热裂解法， 催化加氢法， 但这些方法还没有得到实际应用。
物理吸附法，在吸附剂存在的条件下，含酸原油或馏份进行在 250-350 °C的温度下进行热处理， 可以吸附转移原油中的含酸化合物， 吸附剂可以 采用废催化裂化催化剂。 或者在 100-300°C加热原油和碱土金属氧化物的 混合物， 使碱土金属的氧化物与原油中的有机酸或硫化物反应， 生成碱土 金属碳酸盐和碱土金属硫化物的沉淀，分离后得到脱除环烷酸和硫化物的 原油。
催化加氢法， 采用栽体为氧化铝的 Ni-Mo或 Ni-Co加氢精制催化剂， 在氢分压为 2-3MPa和反应温度为 250°C的条件下加氢处理含酸原油， 使 环烷酸分解为 CO、 C02、 H20和低分子量的石油烃， 可将原油总酸值由 2.6mgKOH/g降为 0.15KOH/g。 催化加氢法是脱酸效果较好， 但需要耐高 压高温设备， 还需氢气， 其设备投资高， 工艺投资大。 在无氢气存在的条 件下， 采用 Ni-Mo或 Ni-Co加氢精制催化剂在 285-345°C的温度下处理高 酸原油， 可将原油的总酸值由 4.0mgKOH/g降为 1.8mgKOH/g。
热处理、 热裂解法（包括催化热裂解法）， US 5891325公开了一种采 用多级热处理的方法降低原油中的酸值的方法。 该方法采用多级热反应， 每级热反应在一定温度和压力下分解部分石油酸，反应生成可挥发的有机 酸、 可挥发的石油烃和不可挥发的石油烃。 在反应的同时用惰性气体吹扫 反应体系，收集可挥发组分，并用 IIA族碱金属盐如 CaO、Ca(OH)2、CaC03、 MgO 等中和可挥发组分中的大部分有机酸， 得到可挥发的石油烃。 然后 将可挥发的石油烃和不挥发的石油烃混合得到脱除了石油酸的原油。
CN 1827744 A公开了一种加工高酸值原油的方法， 是使预处理后的总 酸值大于 0.5mgKOH/g 的原油经预热后注入流化催化裂化反应器中与催 化剂接触， 并在催化裂化反应条件下进行反应， 原油中的环烷酸被裂化为 烃和 co2， 分离反应后的油气和催化剂， 反应油气送至后续分离系统， 而 反应后的催化剂经汽提、 再生后循环使用。
目前， 加工含酸劣质原油普遍的做法是和低酸原油进行混炼， 一般要 求混合原油的酸值不超过 0.5mgKOH/g, 因此含酸原油的掺炼比例受到一 定的限制。 含酸原油的酸值越高， 原油密度越大， 残炭越高， 其加工难度 越大。 发明内容
本发明的目的是在现有技术的基础上， 提供一种将含酸劣质原油， 特 别是酸值超过 0.5mgKOH/g 的原油直接催化裂化生产高附加值产品的催 化剂、 制备所述催化剂的方法、 及使用该催化剂的对所述原油进行转化方 法。
本发明提供的含酸劣质原油转化催化剂， 以催化剂总量为基准， 该催 化剂含有 l-50w%的中孔材料、 l-60w%的分子筛、 5-98w%的耐热无机氧 化物和 0-70 ％的粘土。 优选地， 以催化剂总量为基准， 该催化剂含有 5-40w%的中孔材料、 10-50vv%的分子筛、 10-70vv%的耐热无机氧化物、 0-60 ％的粘土。 更优选地， 以催化剂总量为基准，该催化剂含有 10-40w% 的中孔材料和 20-40w%的分子筛。
本发明所用的催化剂包括中孔材料，该中孔材料为含有碱土金属氧化 物、 氧化硅和氧化铝的无定形材料， 以氧化物的重量百分比计， 其无水化 学表达式为： ( 0-0.3 ) Na20- ( 1-50 ) ΜΟ· ( 6-58 ) Α1203· ( 40-92 ) Si02。 优选地， 以氧化物的重量百分比计， 所述中孔材料的无水化学表达式为 ( 0-0.2 ) Na20- ( 2-30 ) ΜΟ· ( 6-35 ) Α1203' ( 60-92 ) Si02。 M选自 Mg、 Ca和 Ba中的一种或几种、 优选 Mg和 /或 Ca。 所述中孔材料的比表面积 为 200-400m2/g, 孔容为 0.5-2.0ml/g, 优选为 1.0-2.0ml/g; 平均孔径为 8-20nm, 优选为 10-20nm; 最可几孔径为 5-15nm, 优选为 10-15nm。
优选地， 以氧化物的重量百分比计， 无水形式的所述中孔材料中含有 0.1-0.2 %的 Na20, 60-85 %的 Si02和 6-20%的 A1203。 优选地， 以氧化物 的重量百分比计， 无水形式的所述中孔材料中含有 5-30 %的 MO。
所述的分子筛选自八面沸石、 Beta沸石、 具有 MFI结构的分子筛和 丝光沸石中的一种或几种的混合物； 所述的耐热无机氧化物选自氧化铝、 氧化硅和无定型硅铝中的一种或几种的混合物； 所述的粘土选自高岭土、 多水高岭土、 蒙脱土、 硅藻土、 埃洛石、 皂石、 累托土、 海泡石、 凹凸棒 石、 水滑石和膨润土中的一种或几种的混合物。
所述中孔材料的制备方法， 包括将铝源、 硅源与碱土溶液在室温至
85°C下中和成胶， 并采用酸或碱调节成胶终点 pH为 7-9， 在室温至 90°C 下老化 1-10 小时， 将所得固体沉淀物进行铵交换除去杂质离子， 得到铵 交换的凝胶， 或者进一步进行干燥和焙烧。 本发明提供的中孔材料的制备 方法中， 所述的铝源选自硝酸铝、 硫酸铝、 氯化铝和偏铝酸钠中的一种或 几种； 所述的硅源选自水玻璃、 硅酸钠、 四乙基硅和氧化硅中的一种或几 种； 所述的酸选自疏酸、盐酸和硝酸中的一种或几种； 所述的碱选自氨水、 氢氧化钾和氢氧化钠中的一种或几种。 和 /或其前身物及水混合打浆， 加入或不加入粘土， 加入中孔材料， 加入 分子筛， 干燥得到的浆液， 然后焙烧， 其中， 在加入中孔材料前， 加入粘 土前或后，还加入一种酸使浆液的 pH值为 1-5 , 并在 30-90°C的温度下老 化 0.1-10小时； 老化后加入剩余的耐热无机氧化物和 /或其前身物； 所述 中孔材料为如前面所述的含碱土金属氧化物、氧化硅和氧化铝的无定形材 料， 其中， 各组分的可选含量如前对于中孔材料所述。 各组分的用量使最 终催化剂中含有， 以催化剂总量为基准， l-50w%的中孔材料、 l-60w0/。的 分子筛、 5-98w%的耐热无机氧化物和 0-7(½%的粘土。 优选地， 以催化剂 总量为基准， 该催化剂含有 5-40w%的中孔材料、 10-50w%的分子筛、 10-70w%的耐热无机氧化物、 0-60>^%的粘土。 更优选地， 以催化剂总量为 基准， 该催化剂含有 10-4(½%的中孔材料和 20-4(½%的分子筛。
本发明提供的催化剂及其制备方法的有益效果体现在：
由于本发明提供的催化剂含有一种含碱土金属氧化物、氧化硅和氧化 铝的中孔材料， 其比表面积为 200-400m2/g， 孔容为 0.5-2.0ml/g, 平均孔 径为 8-20nm， 其中碱土金属氧化物的存在有利于促进含酸劣质原油中有 机酸的催化分解， 同时高比表面积、 大孔容和中孔孔径有利于含酸劣质原 油中重金属螯合物和胶质分子的进入和吸附，减少因重金属沉积和结焦造 成催化剂活性中心的失活。 因此， 本发明提供的催化剂可以直接催化裂化 含酸劣质原油生产高附加值产品， 同时反应产品如汽油、 柴油的酸值或酸 度符合产品要求， 不需要因酸值或酸度高而对产品进行精制。
本发明提供的将含酸劣质原油催化转化方法包括： 将预处理后的原料 油经预热后注入流化催化裂化反应器中， 与如前所述的催化剂接触、在催 化裂化反应条件下进行反应， 分离反应后的油气和待生催化剂， 反应后的 油气送至后续分离系统，而反应后的待生催化剂经汽提、再生后循环使用； 所使用催化剂的组分及其含量如前面所描述。 其中， 所述中孔材料为前面 所述含碱土金属氧化物、 氧化硅和氧化铝的无定形材料， 其中， 各组分的 可选含量如前对于中孔材料所述。
本发明所提供的原油催化转化方法的有益效果体现在：
本发明提供的方法采用的催化剂中含有一种含碱土金属氧化物、氧化 硅和氧化铝的中孔材料， 其比表面积为 200-400m2/g, 孔容为 0.5-2.0ml/g， 平均孔径为 8-20nm， 其中碱土金属氧化物的存在有利于促进含酸劣质原 油中有机酸的催化分解， 同时高比表面积、 大孔容和中孔孔径有利于含酸 劣质原油中重金属螯合物和胶质分子的进入和吸附，减少因重金属沉积和 结焦造成催化剂活性中心的失活。 因此， 本发明提供的方法有利于直接催 化裂化含酸劣质原油， 生产高附加值的清洁汽油和低碳烯烃产品。 具体实施方式
本发明提供的催化剂含有一种中孔材料、 分子筛、 耐热无机氧化物， 含或不含粘土， 以催化剂总量为基准， 中孔材料的含量为 l-50w%、 分子 筛的含量为 l -60w%、 耐热无机氧化物的含量为 5-98w%、 粘土的含量为 0-70w%。 优选情况下， 中孔材料的含量为 5-40w%、 分子筛的含量为 10-50w% 耐热无机氧化物的含量为 10-70w%、 粘土的含量为 0-60w%。 更优选地， 以催化剂总量为基准， 该催化剂含有 10-40>v%的中孔材料和 20-40w%的分子筛。
所述的中孔材料为含碱土金属氧化物、 氧化硅和氧化铝的无定形材 料，以氧化物的重量百分比计，其无水化学表达式为： （ 0-0.3 )Na2CK 1-50 ) ΜΟ· ( 6-58 ) Α1203· ( 40-92 ) Si〇2, 优选情况下， 其无水化学表达式为： ( 0-0.2 ) Na20- ( 2-30 ) ΜΟ· ( 6-35 ) Α1203· ( 60-92 ) Si02。 优选地， 以氧 化物的重量百分比计，无水形式的所述中孔材料中含有 0.1-0.2 %的 Na20， 60-85 %的 Si〇2和 6-20%的 A1203。 优选地， 以氧化物的重量百分比计， 无水形式的所述中孔材料中含有 5-30 %的 MO。 所述的碱土金属 M选自 Mg、 Ca和 Ba中的一种或几种， 优选 Mg和 /或
Ca。
本发明提供的催化剂中，所述的分子 选自常用作裂化催化剂活性组 分的大孔和中孔分子筛中的一种或几种的混合物，如八面沸石、 Beta沸石、 具有 MFI结构的分子筛和丝光沸石中的一种或几种的混合物。
其中所说的八面沸石为 HY、 REY、 REHY、 USY、 REUSY、 DASY、 DOSY 和 REDASY中的一种或几种的混合物。其中 REY、REHY、REUSY、 REDASY、 DOSY的稀土含量 (以 RE203计）为 0·5-20νν%。
其中所说的八面沸石还可为经 Ba、 Ca、 Fe、 Mg、 P、 Sr、 Sn、 Sb、 Ti、 Zn、 Zr等一种或多种元素改性的 HY、 REY、 REHY USY、 REUSY, DASY、 DOSY和 REDASY中的一种或几种的混合物。其中 REY、 REHY、 REUSY、 REDASY, DOSY的稀土含量 (以 RE203计)为 0.5-20w%。
其中所说的 MFI结构的分子筛为 ZSM-5和 ZRP系列分子筛中的一种 或几种的混合物。
其中所说的 MFI结构的分子筛还可为经 RE、 P、 Fe、 Co、 Ni、 Cu、
Zn、 Mo、 Mn、 Ga、 Sn等一种或多种元素改性的 ZSM-5和 ZRP系列分子 筛中的一种或几种混合物。
其中所说的 Beta沸石还可为经 RE、 P、 Fe、 Co、 Ni、 Cu、 Mn、 Zn 和 Sn等一种或几种元素改性的 Beta沸石。
本发明提供的催化剂中，所述的耐热无机氧化物选自用作裂化催化剂 基质和粘结剂组分的耐热无机氧化物中的一种或几种， 如氧化铝、 氧化硅 和无定型硅铝中的一种或几种。这些耐热无机氧化物为本领域技术人员所 公知。
所述的粘土选自用作裂化催化剂活性组分的粘土中的一种或几种的 混合物， 如高岭土、 多水高岭土、 蒙脱土、 硅藻土、 埃洛石、 皂石、 累托 土、 海泡石、 凹凸棒石、 水滑石和膨润土中的一种或几种的混合物。其中， 优选高岭土、 多水高岭土和蒙脱土中的一种或几种的混合物。 这些粘土为 本领域技术人员所公知。
本发明提供的催化剂的制备方法， 在老化前， 可以将耐热无机氧化物 和 /或其前身物全部加入或部分加入， 为了使催化剂具有更好的耐磨性能， 优选在老化前， 先加入部分耐热无机氧化物和 /或其前身物， 老化后再加 入剩余的耐热无机氧化物和 /或其前身物， 先加入的部分与后加入的部分 使催化剂中先加入的耐热无机氧化物与后加入的耐热无机氧化物的重量 比为 1 : ( 0.1 -10 ) 、 优选 1 : ( 0.1-5 ) 。
本发明提供的催化剂制备方法中，所述的粘土可以在老化前或老化后 加入， 所述粘土加入的顺序对催化剂的性能没有影响。
本发明提供的催化剂制备方法中， 在加入中孔材料前， 加入粘土前或 后，还加入一种酸使浆液的 pH值为 1 -5 ,并在 30-90°C的温度下老化 0.1-10 小时。 所述的酸选自可溶于水的无机酸和有机酸中的一种或几种， 优选为 盐酸、 硝酸、 磷酸和碳原子数为 1-10 的羧酸中的一种或几种的混合物。 酸的用量使桨液的 pH值为 1-5、 优选 1.5-4。
所述老化温度为 30-90°C、 优选 40-80Ό , 老化的时间为 0.1-10小时、 优选 0.5-8小时。
本发明提供的催化剂制备方法中，所述耐热无机氧化物的前身物指在 所述催化剂制备过程中，能形成所述耐热无机氧化物的物质中的一种或几 种。 如氧化铝的前身物可选自水合氧化铝和 /或铝溶胶； 所述水合氧化铝 选自一水软铝石 （薄水铝石） 、 假一水软铝石 （拟薄水铝石） 、 三水合氧 化铝和无定形氢氧化铝中的一种或几种。 氧化硅的前身物可选自硅溶胶， 硅凝胶和水玻璃中的一种或几种。 无定形硅铝的前身物可选自硅铝溶胶， 硅溶胶和铝溶胶的混合物以及硅铝凝胶中的一种或几种。这些耐热无机氧 化物的前身物为本领域技术人员所公知。
本发明提供的催化剂制备方法中， 各组分的用量使最终催化剂中含 有，以催化剂总量为基准， l -50vv%的中孔材料、 l-60w%的分子筛、 5-98>v% 的耐热无机氧化物和 0-70 /。的粘土。 优选情况下， 各组分的用量使最终 催化剂中含有， 以催化剂总量为基准， 5-40w%的中孔材料、 10-50w%的分 子筛、 10-70w%的耐热无机氧化物、 0-60^%的粘土。 更优选地， 以催化剂 总量为基准， 该催化剂含有 10-40w%的中孔材料和 20-40w%的分子筛。
本发明提供的催化剂制备方法中，浆液的干燥方法和条件为本领域技 术人员所公知， 例如， 干燥的方法可以是晾干、 烘干、 鼓风干燥或喷雾干 燥， 优选喷雾干燥。 干燥的温度可以是室温至 400°C， 优选为 100-350°C。 为了便于喷雾干燥， 干燥前浆液的固含量优选为 10-50w%， 更优选为 20-50w%。
所述浆液干燥后的焙烧条件也为本领域技术人员所公知， 一般来说， 所述浆液干燥后的焙烧温度均为 400-700°C、优选 450-65CTC ,焙烧时间至 少为 0.5小时、 优选 0.5-100小时， 更优选为 0.5-10小时。
本发明提供的催化剂制备方法中，所述中孔材料的制备方法包括将铝 源、 硅源与碱土溶液在室温至 85°C下中和成胶， 并采用酸或碱调节成胶 终点 pH为 7-9， 在室温至 90°C下老化 1-10小时， 将所得固体沉淀物进行 铵交换除去杂质离子，得到铵交换的凝胶，还可以进一步进行干燥和焙烧。
其中， 所使用的铝源选自硝酸铝、 硫酸铝、 氯化铝和偏铝酸钠中的一 种或几种的混合物； 所使用的硅源选自水玻璃、 硅酸钠、 四乙基硅和氧化 硅中的一种或几种的混合物； 所使用的酸选自石充酸、 盐酸和硝酸中的一种 或几种的混合物； 所使用的碱选自氨水、 氢氧化钾和氢氧化钠中的一种或 几种的混合物。
其中，所采用的铵交换，是将经老化处理后的固体沉淀物按沉淀物（干 基） ： 铵盐： H20 = 1 : ( 0.1 -1 ) ： ( 10-30 ) 的重量比在室温至 100°C下 交换 1-3次， 每次交换 0.3-1小时， 直至固体沉淀物 （干基） 中钠含量低 于 0.2 %。 交换所用的铵盐选自氯化铵、 硝酸铵、 碳酸铵和碳酸氢铵中的 任一种。
所述中孔材料可以在催化剂制备过程中以凝胶的形式加入，也可以以 干燥或焙烧后的固体形式加入，所述中孔材料的加入形式对催化剂的性能 没有影响。
在本发明所提供的含酸劣质原油催化转化的方法中，使用了如前面所 描述的催化转化催化剂， 该方法包括以下步骤：
将预处理后的原料油经预热后注入催化裂化反应器中，与所述催化剂 接触、在催化裂化反应条件下进行反应，分离反应后的油气和待生催化剂， 反应后的油气送至后续分离系统， 反应后的待生催化剂经汽提、再生后循 环使用
在所述转化方法中，所述的催化裂化反应条件为：反应温度为 450-650
°C， 反应压力为 0.1 -0.8MPa， 重时空速为 5-2511-1， 催化剂与原料油的重量 比为 1 -30。 优选地， 所述的催化裂化反应条件为： 反应温度为 480-60CTC , 反应区的绝压为 0.1-0.5MPa, 空速 10-20^， 催化剂与原料油的重量比为 3-15。
本发明提供的方法中， 优选的方案是将预处理后的原料油预热到
100-280°C后注入催化裂化反应器中， 与催化剂接触、 在催化裂化反应条 件下进行反应。 其中所述的预处理是指：
当所述的原料为含酸原油时， 先将高酸性原油经电脱盐工艺部分脱除 高酸性原油中含有的对催化裂化催化剂具有毒害作用的金属和对催化裂 化装置操作有不利影响的水，脱盐后的原油升温后进入催化裂化反应器中 与再生催化剂接触并反应。
本发明提供的方法中， 所述的原油电脱盐是该专业领域技术人员所熟 知的工艺。 一般的操作方法是将符合电脱盐要求的水与破乳剂和 /或脱金 属剂混合后升温， 再与升温后的高酸原油混合， 混合后的物流进入一级脱 盐罐进行电脱盐后分离出水和油， 分离出的油与含破乳剂和 /或脱金属剂 并经换热器升温的水混合， 然后进入二级脱盐罐。二级脱盐罐分离出的水 和脱盐后的原油。
本发明提供的方法中， 所述原料油的酸值大于 0.5mgKOH/g， 其中重 金属镍和钒的含量之和大于 lOppm, 硫含量大于 lOOOppm, 残碳值高于 3w%。
特性因数 K值是油品的平均沸点和相对密度的函数，其具体关系如下 式： K=(1.216T1/3)/d15.6 15 6， 式中 T为油品平均沸点的绝对温度（K )， 烷烃 的 Κ值最大， 约为 12.7， 环烷烃的次之， 为 11 ~ 12， 芳香烃的 Κ值最小， 为 10 ~ 11。 因此， 特性因数 Κ值可以表征油品的化学属性。
在含酸原油中， 石蜡基原油一般含烷烃量超过 50%, 其特点是密度较 小、 含蜡量较高、 含硫和胶质较少， 特性因数 Κ值大于 12.0; 环烷基原 油的特点是含环烷烃和芳香烃较多， 凝点低， 一般含硫、 含胶质和沥青质 叫多， 特性因数 Κ值小于 11.5; 中间基原油的性质介于这两类之间， 特 性因数 Κ值为 11.5-12.0。
针对不同性质的原油， 优选的两种处理方法为， 对于总酸值大于 0.5mg OH/g, 特性因数 K值小于 12.5的原油， 将预处理后的原油经预热 后引入到催化裂化反应系统中与权利要求 1-7任何之一的催化剂接触， 并 在催化裂化反应条件下进行反应， 分离反应后的油气和待生催化剂， 反应 油气送至分离系统， 得到不同馏程的产物， 将其中的全部或部分柴油引回 到反应系统继续反应； 待生催化剂经汽提、 再生后循环使用。
对于总酸值大于 0.5mgKOH/g, 特性因数 K值大于 12.1的原油，将预 处理后的原油经预热后直接引入催化裂化反应器中与催化剂接触，并在催 化裂化反应条件下进行反应， 分离反应后的油气和待生催化剂， 反应油气 送至后续分离系统， 得到不同馏程的产物； 待生催化剂经汽提、 再生后循 环使用； 所述的催化剂中的分子筛为 Y型分子筛、 具有 MFI结构的分子 筛和任选的 β分子筛。其中以分子筛的总量计， Υ型分子筛的含量为 10 ~ S0wt%,具有 MFI结构的分子筛含量为 10 ~ 90wi%， β分子筛的含量为 0 - 25wi%。
本发明提供的原油转化方法中，所述的催化裂化反应器选自流化床反 应器、提升管反应器、 下行式输送线反应器和移动床反应器中的一种或几 种的组合形式。 其中， 所述提升管反应器选自等直径提升管反应器、 等线 速提升管反应器和变直径提升管反应器中的一种或几种。所述的流化床反 应器选自固定流化床反应器、 散式流化床反应器、 鼓泡床反应器、 湍动床 反应器、 快速床反应器、 输送床反应器和密相流化床反应器中的一种或几 种。
本发明提供的催化剂以及原油转化方法适用于将原油酸值大于 0.5mgKOH/g, 残碳值大于 3w%的含酸劣质原油或其液体馏分直接催化裂 化生产高附加值产品， 同时反应产品如汽油、 柴油的酸值或酸度符合产品 要求， 不需要因酸值或酸度高而对产品进行精制。 优选的， 对于其中原油 酸值大于 lmgKOH/g、 残炭值高于 5w%, Ni含量高于 lOppm , Fe含量高 于 10ppm， Ca含量高于 l Oppm的原油， 本发明提供的催化剂也可以直接 处理， 并具有更好的经济效益。 采用本发明提供的催化剂进行转化处理， 可以有效的降低含酸劣质原油的酸值、 残炭和重金属含量， 使原油的质量 得到提升以便作为催化裂化的原料， 具有更好的经济效益。
下面的实例将对本发明做进一步的说明， 但并不因此而限定本发明。 其中， 中孔材料的无水化学表达式是用 X射线荧光光谱法测定其元素组 成， 再经换算得到。 实施例
实施例和对比例中使用的材料如下：
盐酸由北京化工厂生产， 化学纯， 浓度 36-38w%;
钠水玻璃为市售， 含 Si02浓度为 26.0w%， 模数为 3.2;
多水高岭土由苏州高岭土公司生产， 固含量为 74.0w%；
拟薄水铝石为山东铝厂工业产品， 固含量为 62.0vv%;
铝溶胶为中石化股份公司齐鲁催化剂分公司产品， A1203含量为 21.5w%;
DASY分子筛（固含量为 92.0w°/。）、ZSP-2分子筛（固含量为 97.8w%、 REHY分子筛 （固含量为 88.0w% ) 、 Beta分子筛 （固含量为 95.2w% ) ， DOSY分子筛 （固含量为 93.5w% ) 均由中石化股份公司齐鲁催化剂分公 司生产。
实施例 1 取 1750g浓度为 4w% (以 SiO^† ) 的水玻璃溶液置于烧杯中， 在搅 拌条件下将 350g浓度为 4w% (以 A1203计） 的偏铝酸钠溶液、 150g浓度 为 4w% (以 A1203计）的硫酸铝溶液和 250g浓度为 4w% (以 CaO计）的 氯化钙溶液同时加入到上述水玻璃溶液中， 升温至 80°C老化 4小时； 经 铵离子交换得到凝胶态的中孔材料， 简记为 Nl。
铵离子交换方法： 用 NH4C1溶液按沉淀物（干基）： 铵盐： H20 = 1 : 0.8: 15的重量比在 60°C下对沉淀物进行离子交换以除去其中的钠离子， 交换重复进行两次， 每次进行 0.5小时， 每次交换后进行水洗过滤。
将 N1在 120Ό下干燥 15小时、在 600°C下焙烧 3小时即得中孔材料， 简记为 Gl。 该样品的元素分析重量化学组成为
0.2Na2O-9.8CaO- 19.8Al2O3-70.2SiO2; 其比表面、 孔体积等物化参数均列于 表 1。
实施例 2
本实例说明本发明提供的催化剂中的中孔材料及其制备方法。
在 400g浓度为 2.5w% (以 A1203计） 的硫酸铝溶液中加入 125g浓度 为 4w% (以 CaO计） 的氯化钙溶液， 在搅拌条件下将上述混合溶液加入 到 1700g浓度为 5w% (以 Si02计） 的水玻璃溶液中， 升温至 80°C老化 4 小时； 采用实施例 1 中的方法进行铵离子交换得到凝胶态的中孔材料， 简 记为 N2。 然后在 120°C下干燥 15小时、 在 600°C下焙烧 3小时即得中孔 材料， 简记为 G2。 该样品的元素分析重量化学组成为
0.1Na2O-5.1CaO-9.8Al2O3-85.0SiO2; 其比表面、 孔体积等物化参数均列于 表 1。
实施例 3
本实例说明本发明提供的催化剂中的中孔材料及其制备方法。
取 500g浓度为 4vv% (以 MgO计） 的硫酸镁溶液置于烧杯中， 在搅 拌条件下将 1300g浓度为 5w% (以 Si02计） 的水玻璃溶液加入到上述硫 酸镁溶液中， 再加入 500g浓度为 3>v% (以 A1203计） 的偏铝酸钠溶液， 升温至 80°C老化 4小时； 采用实施例 1 中的方法进行铵离子交换得到凝 胶态的中孔材料， 简记为 N3。 然后在 120°C下干燥 15小时、 在 600°C下 焙烧 3小时即得中孔材料， 简记为 G3。 该样品的元素分析重量化学组成 为 0.1Na2O21.5MgO 12.3Al2O3'66.1SiO2; 其比表面、孔体积等物化参数均 列于表 1。
实施例 4
Figure imgf000014_0001
取 1210g浓度为 5w% (以 SiO^† ) 的水玻璃溶液置于烧杯中， 在搅 拌条件下将 400g浓度为 5w% (以 A1203计） 的偏铝酸钠溶液、 300g浓度 为 5vv% (以 A1203计）的硫酸铝溶液和 450g浓度为 1 w% (以 BaO计）的 硝酸钡溶液同时加入到上述水玻璃溶液中， 升温至 80°C老化 4小时； 采 用实施例 1 中的方法进行铵离子交换得到凝胶态的中孔材料， 简记为 N4。 然后在 120°C下干燥 15小时、 在 600°C下焙烧 3小时即得中孔材料， 简记 为 G4。 该样品的元素分析重量化学组成为
0.1Na2O-4.5BaO-34.8Al2O3-60.6SiO2; 其比表面、孔体积等物化参数均列于 表 1。
实施例 5
本实例说明本发明提供的催化剂中的中孔材料及其制备方法。
取 750g浓度为 4w% (以 MgO计） 的硫酸镁溶液置于烧杯中， 在搅 拌条件下将 1600g浓度为 4w% (以 Si02计） 的水玻璃溶液加入到上述硫 酸镇溶液中， 再加入 150g浓度为 4w% (以 A1203计） 的偏铝酸钠溶液， 升温至 80°C老化 4小时； 采用实施例 1中的方法进行铵离子交换得到凝 胶态的中孔材料， 简记为 N5。 然后在 120°C下干燥 15小时、 在 600°C下 焙烧 3小时即得中孔材料， 简记为 G5。 该样品的元素分析重量化学组成 为 0.1Na2O29.8MgO.6.2Al2O3'63.9SiO2; 其比表面、 孔体积等物化参数均 列于表 1。
实施例 6
Figure imgf000014_0002
在 200g浓度为 3w% (以 A1203计）的硫酸铝溶液中加入 300g浓度为 lw% (以 BaO计） 的硝酸钡溶液， 在搅拌条件下将上述混合溶液加入到 1800g浓度为 5w% (以 Si02计） 的水玻璃溶液中 , 升温至 80°C老化 4小 时； 采用实施例 1中的方法进行铵离子交换得到凝胶态的中孔材料， 简记 为 N6。 然后在 120°C下干燥 15小时、 在 600°C下焙烧 3小时即得中孔材 料， 简记为 G6。 该样品的元素分析重量化学组成为
0. lNa20-3.1 BaO-6.1 Al2O3-90.7SiO2; 其比表面、 孔体积等物化参数均列于 表 1。
表 1
Figure imgf000015_0001
实施例 7
本实例说明本发明提供的催化剂及其制备方法。
取 1.7L盐酸， 用 8.0Kg脱阳离子水进行稀释。 取 7.7Kg钠水玻璃， 加 8.0Kg脱阳离子水进行稀释，搅拌下将稀释过的钠水玻璃緩慢加入上述 盐酸稀溶液中， 得到 Si02浓度 7.8w%, pH值 2.8的硅溶胶。
在上述硅溶胶中加入 3.4Kg多水高岭土，搅拌 lh，使高岭土充分分散。 在 12.5Kg脱阳离子水中加入 3.8KgDASY分子筛， 2.0Kg (干基） 实 施例 1中制备的中孔材料 Gl， 经均质器充分分散后， 用稀盐酸调 pH值 为 3.5。 将分子筛和中孔材料的混合浆液加入到上述硅溶胶-粘土浆液中， 搅拌 0.5h， 得到固含量为 20.8vv%、 pH值为 2.9的催化剂浆液。 将此浆液 于尾气温度 250°C下喷雾成型， 洗涤， 干燥， 焙烧。 得到本发明提供的组 成为 20w%中孔材料、 35w%DASY分子筛、 25w%高岭土、 20w%SiO2粘 结剂的催化剂， 简记为 Cl。
对比例 1 按实例 7的方法制备催化剂， 不同的是不加入中孔材料， 多水高岭土 的用量为 6.1公斤， 得到组成为 35w%DASY分子筛、 45 ^%高岭土、 20vv%SiO2粘结剂的对比催化剂， 简记为 CB 1。
对比例 2
本对比例说明含 V205中孔材料的对比催化剂及其制备方法。
按实例 1的方法制备中孔材料， 不同的是以草酸钒代替氯化钙， 得到 含钒的中孔材料， 简记为 GB1。 该样品的元素分析重量化学组成为
0.2Na2O-9.8V2O5- 19.8Al2O3'70.2SiO2。
按实例 7的方法制备催化剂， 不同的是以含钒的中孔材料 GB1代替 G1 , 得到组成为 20w%含钒的中孔材料、 35w%DASY分子筛、 高岭 土、 20w%SiO2粘结剂的对比催化剂， 简记为 CB2。
对比例 3
本对比例说明含 Ti02中孔材料的对比催化剂及其制备方法。
按实例 1的方法制备中孔材料， 不同的是以四氯化钛代替氯化钙， 得 到含钛的中孔材料， 简记为 GB2。 该样品的元素分析重量化学组成为 0.2Na2O'9.8TiO2 19.8Al2O3'70.2SiO2。
按实例 7的方法制备催化剂 , 不同的是以含钛的中孔材料 GB2代替 G1 , 得到组成为 20w%含钛的中孔材料、 35w%DASY分子筛、 Z w%高冷 土、 20w%SiO2粘结剂的对比催化剂， 简记为 CB3。
实施例 8
本实例说明本发明提供的催化剂及其制备方法。
15公斤脱阳离子水中， 加入 2.7公斤多水高岭土打浆， 再加入 3.2公 斤拟薄水铝石， 用盐酸将其 pH调至 2， 搅拌均勾， 在 70°C下静置老化 1 小时， 加入 2.3公斤铝溶交， 老化前后加入的耐热无机氧化物前身物使老 化前后加入的耐热无机氧化物的重量比为 1 : 0.25 , 搅拌均匀。
在 12.5Kg脱阳离子水中加入 2.0KgDASY分子筛， 0.72KgZSP-2分子 筛， 3.0Kg (干基） 实例 2中制备的中孔材料 G2, 经均质器充分分散后， 用稀盐酸调 pH值为 3.5。 将分子筛和中孔材料的混合浆液加入到上述氧 化铝-粘土浆液中， 搅拌 0.5h， 得到固含量为 24.0 ^%的催化剂浆液， 将得 到的浆液在 250°C的温度下喷雾干燥成型， 洗涤， 干燥， 焙烧。 得到本发 明提供的组成为 30w%中孔材料、 18w%DASY分子筛、 7w%ZSP-2分子筛、 20¼ %高吟土、 25 ν%Α1203粘结剂的催化剂， 简记为 C2。
实施例 9 本实例说明本发明提供的催化剂及其制备方法。
15公斤脱阳离子水中， 加入 3.4公斤多水高岭土打浆， 再加入 3.2公 斤， 用盐酸将其 pH调至 2， 搅拌均匀， 在 70°C下静置老化 1小时， 加入 4.7公斤铝溶胶， 老化前后加入的耐热无机氧化物前身物使老化前后加入 的耐热无机氧化物的重量比为 1 : 0.5 , 搅拌均匀。
在 6Kg脱阳离子水中加入 1.1 KgDAS Y分子筛， 2.1 KgZSP-2分子筛， 经均质器充分分散后， 将分子 浆液加入到上述氧化铝-粘土浆液中， 再 加入 1.5Kg (干基） 实例 2中制备的凝胶态中孔材料 N2， 搅拌 0.5h, 得 到固含量为 21.2vv%的催化剂浆液， 将得到的浆液在 250°C的温度下喷雾 干燥成型， 洗涤， 干燥， 焙烧。 得到本发明提供的组成为 15w%中孔材料、 10w%DASY分子筛、 20w%ZSP-2分子筛、 25 ％高岭土、 30νν%Α12Ο3粘 结剂的催化剂， 简记为 C3。
实施例 10
本实例说明本发明提供的催化剂及其制备方法。
20公斤脱阳离子水中， 加入 4.1公斤多水高岭土打浆， 再加入 4.8公 斤拟薄水铝石， 用盐酸将其 pH调至 2, 搅拌均勾， 在 70°C下静置老化 1 小时。
在 7.5Kg脱阳离子水中加入 2.3KgREHY分子筛， l .lKgBeta分子筛， l .OKg (干基） 实例 3中制备的中孔材料 G3， 经均质器充分分散后， 用稀 盐酸调 pH值为 3.5。 将分子筛和中孔材料的混合浆液加入到上述氧化铝- 粘土浆液中， 搅拌 0.5h, 得到固含量为 24.3w%的催化剂浆液， 将得到的 浆液在 250°C的温度下喷雾干燥成型， 洗涤， 干燥， 焙烧。 得到本发明提 供的组成为 1 (½%中孔材料、20w%REHY分子筛、 10w%Beta分子筛、30w% 高岭土、 30w%Al2O3粘结剂的催化剂， 简记为 C4。
实施例 1 1
本实例说明本发明提供的催化剂及其制备方法。
在 6.0Kg脱阳离子水中加入 3.2KgDOSY分子筛， 经均质器充分分散 后， 加入 4.0Kg (干基） 实例 3中制备的凝胶态中孔材料 N3 , 和 14.0公 斤铝溶胶搅拌均匀， 得到固含量为 17.8vv%的催化剂浆液， 将得到的浆液 在 250°C的温度下喷雾干燥成型， 洗涤， 干燥， 焙烧。 得到本发明提供的 组成为 40w%中孔材料、 30vv%DOSY分子筛、 30w°/。Al2O3粘结剂的催化 剂， 简记为 C5。 实施例 12
本实例说明本发明提供的催化剂及其制备方法。
20公斤脱阳离子水中， 加入 4.1公斤多水高岭土打浆， 再加入 4.0公 斤拟薄水铝石， 用盐酸将其 pH调至 2， 搅拌均匀， 在 70°C下静置老化 1 小时。
在 8.0Kg脱阳离子水中加入 2.2KgDASY分子筛， 2.5Kg (干基）实例 4中制备的中孔材料 G4， 经均质器充分分散后， 用稀盐酸调 pH值为 3.5。 将分子筛和中孔材料的混合浆液加入到上述氧化铝 -粘土浆液中， 搅拌 0.5h, 得到固含量为 24.2 ％的催化剂浆液， 将得到的浆液在 250°C的温度 下喷雾干燥成型， 洗涤， 干燥， 焙烧。 得到本发明提供的组成为 25w%中 孔材料、 20w%DASY分子筛、 30¼%高岭土、 25νν%Α1203粘结剂的催化剂， 简记为 C6。
实施例 13
本实例说明本发明提供的催化剂及其制备方法。
按实例 12的方法制备催化剂， 不同的是以实例 5中制备的中孔材料
G5代替 G4,得到本发明提供的组成为 25w%中孔材料、 20w%DASY分子 筛、 30w%高吟土、 25w%Al203粘结剂的催化剂， 简记为 C7。
实施例 14
本实例说明本发明提供的催化剂及其制备方法。
按实例 12的方法制备催化剂， 不同的是以实例 6中制备的中孔材料
G6代替 G4,得到本发明提供的组成为 25vv%中孔材料、 20w%DASY分子 筛、 30w%高吟土、 25νν%Α1203粘结剂的催化剂， 简记为 C8。
实施例 15
下面的实例说明本发明提供的催化剂的催化性能。
将催化剂 C 1进行金属污染，其污染量为 Fe: 6000ppm, Ni: 9000ppm,
Ca:3000ppm , 然后将污染后的催化剂在 100 %水蒸汽条件下老化 8小时。
在小型固定流化床装置上， 采用表 2所示含酸劣质原油 2对催化剂的 裂化性能进行考察，反应温度为 500 °C，剂油重量比为 5，重时空速为 20^， 反应条件和结果见表 3。
对比例 4-6
下面的对比例说明对比催化剂的催化性能。
按实例 15的方法污染、 老化并评价催化剂的催化性能， 不同的是用 对比例 1-3所述的对比催化剂 CB1、 CB2和 CB3分别代替本发明提供的 催化剂 Cl。 反应条件和结果列于表 3中。
实施例 16-17
下面的实例说明本发明提供的催化剂的催化性能。
将催化剂 C2、 C3在 100 %水蒸汽条件下老化 17小时。在小型固定流 化床装置上，采用表 2所示含酸劣质原油 1对催化剂的裂化性能进行考察， 反应条件和产品分布见表 4。
实施例 18-19
下面的实例说明本发明提供的催化剂的催化性能。
将催化剂 C4、 C5分别进行金属污染， 其污染量为 Fe: 8000ppm, Ni:
12000ppm, Ca:4000ppm, 然后将污染后的催化剂在 100 %水蒸汽条件下 老化 8小时。 在小型固定流化床装置上， 采用表 2所示含酸劣质原油 3对 催化剂的裂化性能进行考察， 反应温度为 500°C， 剂油重量比为 6, 重时 空速为 20小时 反应条件和结果见表 5。
实施例 20-22
下面的实例说明本发明提供的催化剂的催化性能。
将催化剂 C6、 C7、 C8分别进行金属污染， 其污染量为 Fe: 6000ppm, Ni: 9000ppm, Ca:3000ppm, 然后将污染后的催化剂在 100 %水蒸汽条件 下老化 8小时。 在小型固定流化床装置上， 采用表 2所示含酸劣质原油 4 对催化剂的裂化性能进行考察， 反应温度为 520°C , 剂油重量比为 8， 重 时空速为 16小时―1， 反应条件和结果见表 6。
表 2 原料油性质
Figure imgf000020_0001
表 3
Figure imgf000021_0001
表 4
Figure imgf000022_0001
实例编号 实施例 18 实施例 19 催化剂 C4 C5 反应温度， 500 500 剂油重量比 6 6 重时空速， h— 1 20 20 转化率 67.3 69.1 产品分布， 重％
干气 1.2 1.1 液化气 13.9 13.2 汽油 40.7 43.9 柴油 19.9 19.8 重油 12.8 11.1 焦炭 1 1.5 10.9 汽油酸度，
0.1 0.1 mgKOH/ 100ml
柴油酸值，
<0.02 <0.02 mgKOH/g
表 6
Figure imgf000024_0001
由表 3、 表 4、 表 5和表 6可见， 本发明提供的催化剂可以直接催化 裂化酸值大于 0.8mgKOH/g， 胶质含量大于 16.6w%, 同时具有较高金属 含量的含酸劣质原油， 直接生产高附加值产品， 同时反应产品如汽油、 柴 油的酸值或酸度符合产品要求， 不需要因酸值或酸度高而对产品进行精 制。 具有很高的经济效益。

Claims

权 利 要 求
1、 一种含酸劣质原油转化催化剂， 其特征在于以催化剂总量为基准， 该催化剂含有 l-50w%的中孔材料、 l-60w%的分子筛、 5-98^%的耐热无 机氧化物和 0-70¼%的粘土； 其中所述中孔材料为含有碱土金属氧化物、 氧化硅和氧化铝的无定形材料， 以氧化物的重量百分比计， 其无水化学表 达式为： ( 0-0.3 ) Na20- ( 1-50 ) MO' ( 6-58 ) Α1203· ( 40-92 ) Si〇2, 其中， M选自 Mg、 Ca和 Ba中的一种或几种； 其比表面积为 200-400m2/g, 孑 L 容为 0.5-2.0ml/g， 平均孔径为 8-20nm, 最可几孔径为 5-15nm。
2、 按照权利要求 1的催化剂， 其特征在于以氧化物的重量百分比计， 所述中孔材料的无水化学表达式为 ( 0-0.2 ) Na20- ( 2-30 ) ΜΟ· ( 6-35 ) Α1203· ( 60-92 ) Si02。
3、 按照权利要求 1的中孔材料， 其特征在于所述的碱土金属 M选自 Mg和 Ca。
4、 按照权利要求 1的催化剂， 其特征在于以催化剂总量为基准， 该 催化剂含有 5- 40w%的中孔材料、 10-50w%的分子筛、 10-70 ％的耐热无 机氧化物、 0-60w%的粘土。
5、 按照权利要求 4的催化剂， 其特征在于以催化剂总量为基准， 该 催化剂含有 10-4(½%的中孔材料和 20-40^%的分子筛。
6、 按照权利要求 1的催化剂， 其特征在于所述的分子筛选自八面沸 石、 Beta沸石、 具有 MFI结构的分子筛和丝光沸石中的一种或几种的混 合物。
7、 按照权利要求 1的催化剂， 其特征在于所述的耐热无机氧化物选 自氧化铝、 氧化硅和无定型硅铝中的一种或几种的混合物； 所述的粘土选 自高吟土、 多水高岭土、 蒙脱土、 硅藻土、 埃洛石、 皂石、 累托土、 海泡 石、 凹凸棒石、 水滑石和膨润土中的一种或几种的混合物。
8、 权利要求 1的催化剂的制备方法， 其特征在于该方法包括将全部 或部分耐热无机氧化物和 /或其前身物及水混合打浆， 加入或不加入粘土， 加入中孔材料， 加入分子 ， 干燥得到的浆液， 然后焙烧， 其中， 在加入 中孔材料前， 加入粘土前或后， 还加入一种酸使浆液的 pH值为 1-5， 并 在 30-90°C的温度下老化 0.1-10小时； 老化后加入剩余的耐热无机氧化物 和 /或其前身物， 各组分的用量使最终催化剂中含有， 以催化剂总量为基 准， l-50w%的中孔材料、 l -60w%的分子筛、 5- 98w%的耐热无机氧化物和 0-7(½%的粘土。 '―
9、 按照权利要求 8的方法， 其特征在于在老化前， 先加入部分耐热 无机氧化物和 /或其前身物， 老化后再加入剩余的耐热无机氧化物和 /或其 前身物，先加入的部分与后加入的部分使催化剂中先加入的耐热无机氧化 物与后加入的耐热无机氧化物的重量比为 1 : ( 0.1-10 ) 。
10、 使用权利要求 1-7任何之一的催化转化催化剂来进行含酸劣质原 油催化转化的方法， 将预处理后的原料油经预热后注入催化裂化反应器 中， 与权利要求 1-7任何之一的催化剂接触、 在催化裂化反应条件下进行 反应，分离反应后的油气和待生催化剂，反应后的油气送至后续分离系统， 反应后的待生催化剂经汽提、 再生后循环使用。
1 1、 按照权利要求 10的方法， 其特征在于将预处理后的原料油预热 到 100-250°C后注入催化裂化反应器中， 与所述催化剂接触、 在催化裂化 反应条件下进行反应。
12、 按照权利要求 11 的方法， 其特征在于将预处理后的总酸值大于
0.5mgKOH/g,特性因数 K值小于 12.5的原油经预热后引入到催化裂化反 应系统中与所述催化剂接触， 并在催化裂化反应条件下进行反应， 分离反 应后的油气和待生催化剂，反应油气送至分离系统，得到不同馏程的产物， 将其中的全部或部分柴油引回到反应系统继续反应； 待生催化剂经汽提、 再生后循环使用。
13、 按照权利要求 11 的方法， 其特征在于将预处理后的总酸值大于 0.5mgKOH/g,特性因数 K值大于 12.1的原油经预热后直接引入催化裂化 反应器中与催化剂接触， 并在催化裂化反应条件下进行反应， 分离反应后 的油气和待生催化剂，反应油气送至后续分离系统，得到不同镏程的产物； 待生催化剂经汽提、 再生后循环使用； 所述的催化剂中的分子筛含有 Y 型分子筛、 具有 MFI结构的分子筛和任选的 β分子筛， 其中以分子筛的 总量计， Υ型分子筛的含量为 10 ~ 80w %， 具有 MFI结构的分子筛含量 为 10 ~ 90w?%， β分子筛的含量为 0 ~ 25wi%。
14、 按照权利要求 10-13任何之一的方法， 其特征在于在所述的催化 裂化反应条件为： 反应温度为 450-650°C , 反应压力为 0.1-0.8MPa， 重时 空速为 5-25^ , 催化剂与原料油的重量比为 1-30。
15、 按照权利要求 14的方法， 其特征在于所述的催化裂化反应条件 为： 反应温度为 480-600°C， 反应区的绝压为 0.1-0.5MPa, 空速 10-20^， 催化剂与原料油的重量比为 3-15。
16、 按照权利要求 1 1、 12或 13的方法， 其特征在于所述原料油的酸 值大于 1.0mgKOH/g， 其中重金属镍和钒的含量之和大于 lOppm, 硫含量 大于 lOOOppm, 残碳值高于 5w%。
PCT/CN2009/000032 2008-01-09 2009-01-09 含酸劣质原油转化催化剂及其制备方法和应用 Ceased WO2009092282A1 (zh)

Priority Applications (4)

Application Number Priority Date Filing Date Title
BRPI0907160-1A BRPI0907160B1 (pt) 2008-01-09 2009-01-09 Catalyst for converting lower gross oil containing acid, processes for preparing the same and to convert catalytically lower gross oil containing acid with use of conversion catalyst
JP2010541682A JP5622588B2 (ja) 2008-01-09 2009-01-09 粗悪な酸含有原油用変換触媒、当該触媒の製造方法及び当該触媒の利用
CA2711392A CA2711392C (en) 2008-01-09 2009-01-09 Catalyst for converting inferior acid-containing crude oil, process for manufacturing the same, and application thereof
US12/812,148 US8809216B2 (en) 2008-01-09 2009-01-09 Catalyst for converting acid-containing inferior crude oil and process for making and using the same

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
CN200810055793.1 2008-01-09
CN2008100557931A CN101480621B (zh) 2008-01-09 2008-01-09 一种含酸劣质原油转化催化剂及其制备方法
CN200810112001XA CN101586038B (zh) 2008-05-20 2008-05-20 一种含酸劣质原油催化转化方法
CN200810112001.X 2008-05-20

Publications (1)

Publication Number Publication Date
WO2009092282A1 true WO2009092282A1 (zh) 2009-07-30

Family

ID=40900768

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2009/000032 Ceased WO2009092282A1 (zh) 2008-01-09 2009-01-09 含酸劣质原油转化催化剂及其制备方法和应用

Country Status (6)

Country Link
US (1) US8809216B2 (zh)
JP (1) JP5622588B2 (zh)
KR (1) KR101540680B1 (zh)
BR (1) BRPI0907160B1 (zh)
CA (1) CA2711392C (zh)
WO (1) WO2009092282A1 (zh)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101207661B1 (ko) 2010-07-21 2012-12-03 (주)포스코켐텍 원유 방제용 방제제, 그 제조방법 및 원유 방제 방법
CN103260747A (zh) * 2010-11-16 2013-08-21 罗地亚管理公司 氧化铝催化剂载体
US9259711B2 (en) 2008-05-20 2016-02-16 China Petroleum & Chemical Corporation Catalyst for upgrading inferior acid-containing crude oil, process for manufacturing the same, and application thereof
CN108740692A (zh) * 2018-05-14 2018-11-06 中国标准化研究院 食品用干燥剂及其制备方法

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103372427B (zh) * 2012-04-28 2015-05-20 中国石油化工股份有限公司 一种重质油接触裂化-焦炭气化催化剂及其制备方法
JP5925100B2 (ja) * 2012-10-03 2016-05-25 本田技研工業株式会社 ポリプロピレン組成物の製造方法
EP2919907B1 (en) 2012-12-21 2023-12-06 Albemarle Europe Sprl. Modified y-zeolite/zsm-5 catalyst for increased propylene production
US20140378718A1 (en) * 2013-06-24 2014-12-25 Baker Hughes Incorporated Method for reducing acids in crude oil
CN106582842A (zh) * 2016-12-14 2017-04-26 钦州学院 一种劣质原油改质催化剂及其制备方法
CN114425399B (zh) * 2020-09-24 2023-09-05 中国石油化工股份有限公司 一种催化裂化催化剂及其制备方法与应用
CN114471689B (zh) * 2020-10-28 2023-09-01 中国石油化工股份有限公司 一种加氢裂化催化剂的制备方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0313167A1 (en) * 1987-10-23 1989-04-26 Nippon Oil Company, Limited Catalysts for converting hydrocarbons
WO2004020093A1 (en) * 2002-08-29 2004-03-11 Albemarle Netherlands B.V. Catalyst for the production of light olefins
CN1504540A (zh) * 2002-11-29 2004-06-16 中国石油化工股份有限公司 一种石油烃裂解制取低碳烯烃的催化剂
CN1552805A (zh) * 2003-05-30 2004-12-08 �й�ʯ�ͻ����ɷ����޹�˾ 一种含分子筛的烃类裂化催化剂及其制备方法

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4994254A (en) * 1986-01-09 1991-02-19 Research Association For Utilization Of Light Oil Aluminogallosilicates of the mfi type
US6211104B1 (en) * 1997-10-15 2001-04-03 China Petrochemical Corporation Catalyst for catalytic pyrolysis process for the production of light olefins and the preparation thereof
US5891325A (en) * 1998-08-11 1999-04-06 Exxon Research And Engineering Co. Process for reducing total acid number of crude oil
JP2000119014A (ja) * 1998-08-12 2000-04-25 Fuji Chem Ind Co Ltd 無晶形ケイ酸アルミン酸カルシウム複合酸化物及びその製造方法並びに制酸剤
US6346224B1 (en) * 1999-10-22 2002-02-12 Intevep, S.A. Metaloalluminosilicate composition, preparation and use
TWI277648B (en) * 2004-07-29 2007-04-01 China Petrochemical Technology A cracking catalyst for hydrocarbons and its preparation
CN100363467C (zh) * 2005-03-03 2008-01-23 中国石油化工股份有限公司 一种加工高酸值原油的方法
CN1978593B (zh) * 2005-11-30 2010-12-01 中国石油化工股份有限公司 一种裂化催化剂
CN1986505B (zh) * 2005-12-23 2010-04-14 中国石油化工股份有限公司 一种增产低碳烯烃的催化转化方法
JP5188034B2 (ja) * 2006-04-27 2013-04-24 旭化成ケミカルズ株式会社 耐磨耗性に優れた機能を有する金担持粒子
DE102006040432A1 (de) * 2006-08-29 2008-03-20 Oxeno Olefinchemie Gmbh Katalysator und Verfahren zur Herstellung von Isoolefinen
CN101134172B (zh) * 2006-08-31 2010-10-27 中国石油化工股份有限公司 一种烃类转化催化剂
CN101134913B (zh) * 2006-08-31 2011-05-18 中国石油化工股份有限公司 一种烃类催化转化方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0313167A1 (en) * 1987-10-23 1989-04-26 Nippon Oil Company, Limited Catalysts for converting hydrocarbons
WO2004020093A1 (en) * 2002-08-29 2004-03-11 Albemarle Netherlands B.V. Catalyst for the production of light olefins
CN1504540A (zh) * 2002-11-29 2004-06-16 中国石油化工股份有限公司 一种石油烃裂解制取低碳烯烃的催化剂
CN1552805A (zh) * 2003-05-30 2004-12-08 �й�ʯ�ͻ����ɷ����޹�˾ 一种含分子筛的烃类裂化催化剂及其制备方法

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9259711B2 (en) 2008-05-20 2016-02-16 China Petroleum & Chemical Corporation Catalyst for upgrading inferior acid-containing crude oil, process for manufacturing the same, and application thereof
KR101207661B1 (ko) 2010-07-21 2012-12-03 (주)포스코켐텍 원유 방제용 방제제, 그 제조방법 및 원유 방제 방법
CN103260747A (zh) * 2010-11-16 2013-08-21 罗地亚管理公司 氧化铝催化剂载体
JP2014500217A (ja) * 2010-11-16 2014-01-09 ロディア オペレーションズ アルミナ触媒担体
US9731286B2 (en) 2010-11-16 2017-08-15 Rhodia Operations Alumina catalyst support
CN108740692A (zh) * 2018-05-14 2018-11-06 中国标准化研究院 食品用干燥剂及其制备方法

Also Published As

Publication number Publication date
US8809216B2 (en) 2014-08-19
KR101540680B1 (ko) 2015-07-30
CA2711392A1 (en) 2009-07-30
JP5622588B2 (ja) 2014-11-12
BRPI0907160A2 (pt) 2015-07-07
KR20100103658A (ko) 2010-09-27
JP2011509178A (ja) 2011-03-24
US20100288675A1 (en) 2010-11-18
BRPI0907160B1 (pt) 2017-12-12
CA2711392C (en) 2017-02-07

Similar Documents

Publication Publication Date Title
WO2009092282A1 (zh) 含酸劣质原油转化催化剂及其制备方法和应用
RU2418842C2 (ru) Способ каталитической конверсии углеводородов
CA2563262C (en) A zeolite-containing hydrocarbon-converting catalyst, the preparation process thereof, and a process for converting hydrocarbon oils with the catalyst
JP5587297B2 (ja) 含酸劣質原油改質触媒、その製造方法、およびその応用
WO2009111953A1 (zh) 一种从劣质原料油制取轻质燃料油的方法
AU2002365129C1 (en) FCC catalysts for feeds containing nickel and vanadium
CN104946301B (zh) 一种提高低碳烯烃浓度的催化转化方法
CN107971012A (zh) 一种生产低碳烯烃和轻芳烃的催化裂解方法
CN100497530C (zh) 一种烃油裂化方法
CN105505455B (zh) 一种页岩油催化裂化的加工方法
CN101584984A (zh) 一种劣质原油催化改质催化剂及其制备方法
CN101586038B (zh) 一种含酸劣质原油催化转化方法
CN101480621B (zh) 一种含酸劣质原油转化催化剂及其制备方法
CN101591551B (zh) 一种劣质原油的催化改质方法
CN100389176C (zh) 一种增产丙烯的裂化助剂
CN103506152B (zh) 一种处理加氢处理原料油的催化剂
CN102051227B (zh) 一种多产柴油和丙烯的催化转化方法
CN102031138A (zh) 一种多产柴油和丙烯的催化转化方法
CN111040807B (zh) 一种采用双提升管进行加工劣质油的方法和系统
CN103509588B (zh) 一种针对多含环烷环的原料油多产低碳烯烃和轻芳烃的裂化方法
CN102108308B (zh) 原油生产高辛烷值汽油的催化转化方法
CN102079995B (zh) 一种原油生产优质轻质燃料的催化转化方法
CN121198342A (zh) 废塑料油催化转化用催化剂组合物及其制备方法与应用、废塑料油催化裂解生产低碳烯烃的方法
JP2008173529A (ja) 炭化水素油の接触分解触媒及び該触媒を用いる炭化水素油の接触分解方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 09703649

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2711392

Country of ref document: CA

WWE Wipo information: entry into national phase

Ref document number: 4848/DELNP/2010

Country of ref document: IN

WWE Wipo information: entry into national phase

Ref document number: 12812148

Country of ref document: US

Ref document number: 2010541682

Country of ref document: JP

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 20107017074

Country of ref document: KR

Kind code of ref document: A

32PN Ep: public notification in the ep bulletin as address of the adressee cannot be established

Free format text: NOTING OF LOSS OF RIGHTS PURSUANT TO RULE 112(1) EPC (EPO FORM 1205A DATED 29.10.2010)

122 Ep: pct application non-entry in european phase

Ref document number: 09703649

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: PI0907160

Country of ref document: BR

Kind code of ref document: A2

Effective date: 20100709