CN114425394A - Regeneration method of inactivated light alkane isomerization catalyst - Google Patents
Regeneration method of inactivated light alkane isomerization catalyst Download PDFInfo
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- CN114425394A CN114425394A CN202011187130.2A CN202011187130A CN114425394A CN 114425394 A CN114425394 A CN 114425394A CN 202011187130 A CN202011187130 A CN 202011187130A CN 114425394 A CN114425394 A CN 114425394A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 221
- 238000006317 isomerization reaction Methods 0.000 title claims abstract description 67
- 150000001335 aliphatic alkanes Chemical class 0.000 title abstract description 18
- 238000011069 regeneration method Methods 0.000 title abstract description 13
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 49
- 239000001257 hydrogen Substances 0.000 claims abstract description 45
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 45
- 239000012188 paraffin wax Substances 0.000 claims abstract description 42
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 41
- 230000009467 reduction Effects 0.000 claims abstract description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000001301 oxygen Substances 0.000 claims abstract description 15
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 15
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 57
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 39
- 239000000460 chlorine Substances 0.000 claims description 35
- 229910052799 carbon Inorganic materials 0.000 claims description 29
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 28
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 27
- 229910052801 chlorine Inorganic materials 0.000 claims description 23
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 21
- 229910052697 platinum Inorganic materials 0.000 claims description 19
- 229910052757 nitrogen Inorganic materials 0.000 claims description 18
- 239000012159 carrier gas Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000005262 decarbonization Methods 0.000 claims description 5
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 3
- 230000001172 regenerating effect Effects 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical class Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 15
- 229930195733 hydrocarbon Natural products 0.000 description 15
- 150000002430 hydrocarbons Chemical class 0.000 description 15
- 230000008569 process Effects 0.000 description 15
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 12
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 12
- 239000004215 Carbon black (E152) Substances 0.000 description 11
- 239000002994 raw material Substances 0.000 description 9
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 8
- 238000010926 purge Methods 0.000 description 8
- 230000003213 activating effect Effects 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 6
- 230000004913 activation Effects 0.000 description 5
- 230000008929 regeneration Effects 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000009849 deactivation Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000006073 displacement reaction Methods 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- HNRMPXKDFBEGFZ-UHFFFAOYSA-N 2,2-dimethylbutane Chemical compound CCC(C)(C)C HNRMPXKDFBEGFZ-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- GJEAMHAFPYZYDE-UHFFFAOYSA-N [C].[S] Chemical compound [C].[S] GJEAMHAFPYZYDE-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000001833 catalytic reforming Methods 0.000 description 1
- 238000004737 colorimetric analysis Methods 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 150000003058 platinum compounds Chemical class 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 230000002000 scavenging effect Effects 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
Classifications
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- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/28—Regeneration or reactivation
- B01J27/32—Regeneration or reactivation of catalysts comprising compounds of halogens
-
- 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
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/02—Heat treatment
-
- 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
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
- B01J38/10—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst using elemental hydrogen
-
- 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
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
- B01J38/12—Treating with free oxygen-containing gas
- B01J38/14—Treating with free oxygen-containing gas with control of oxygen content in oxidation gas
-
- 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
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
- B01J38/42—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst using halogen-containing material
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
- C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
- C07C5/2767—Changing the number of side-chains
- C07C5/277—Catalytic processes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/06—Halogens; Compounds thereof
- C07C2527/128—Compounds comprising a halogen and an iron group metal or a platinum group metal
- C07C2527/13—Platinum group metals
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to a regeneration method of a deactivated light paraffin isomerization catalyst, which comprises the following steps: roasting the inactivated light alkane isomerization catalyst in an oxygen-containing atmosphere to obtain a roasted catalyst; make H2With catalysis after calcinationCarrying out reduction treatment by agent contact to obtain a catalyst after reduction treatment; carrying out pre-chlorination treatment on the reduced catalyst by using hydrogen containing HCl to obtain a pre-chlorinated catalyst; under the condition of hydrogen, AlCl is reacted3Contacting with the catalyst after the pre-chlorination treatment to perform chlorination treatment. The method of the invention can effectively recover the performance of the deactivated light paraffin isomerization catalyst.
Description
Technical Field
The invention relates to a regeneration method of a deactivated catalyst, in particular to a regeneration method of a deactivated light alkane isomerization catalyst.
Background
The Pt-containing alumina is a very important hydrocarbon conversion catalyst and is widely applied to petroleum refining and petrochemical processes, such as catalytic reforming, light alkane isomerization, low-carbon alkane dehydrogenation and the like. Such catalysts generally have high catalytic activity and selectivity, but have the disadvantage of being relatively sensitive to impurities, with Pt-containing chlorided alumina catalysts being most typical.
The Pt-containing chloridized alumina catalyst is a bifunctional catalyst which takes alumina as a carrier and loads noble metals Pt and Cl. Pt is the metal center of the catalyst, Cl is the acid center of the catalyst, and in order to ensure the strong acid function of the catalyst and ensure that the catalyst has higher catalytic activity at a low temperature of not more than 200 ℃, the Cl content in the catalyst is generally higher than 3.5 mass percent. The Pt-containing aluminum chloride oxide catalyst is mainly used for catalyzing light alkane isomerization reaction, although reaction raw materials need to be strictly refined before contacting the catalyst, the activity of the catalyst also gradually decreases along with the prolonging of the running time of the catalyst, and the main reasons of the activity decrease comprise the damage of trace water in the raw materials to the acid center of the catalyst, the adsorption of heavy hydrocarbons in the raw materials on the active center of the catalyst, the carbon deposit of the catalyst and the like. When the activity of the catalyst decreases to the point where product quality or plant economy is affected, it is necessary to replace the fresh catalyst or to activate or regenerate the deactivated catalyst. The proper catalyst activating or regenerating method can restore the performance of deactivated catalyst and has the advantages of low cost, short period, etc. compared with replacing new catalyst.
GB969863A discloses an improved catalyst regeneration process in which a deactivated catalyst is calcined in an oxygen-containing atmosphere and then re-chlorinated, the chlorination being carried out by reacting a chlorine-containing organic compound of a given structure with the calcined catalyst in air. The method is suitable for regenerating the Pt-containing chloridized alumina catalyst. However, the Pt in the regenerated catalyst obtained by the method is easy to lose, and the Pt is in an oxidation state, although the isomerization reaction is hydrogen, only part of Pt is reduced due to low reaction temperature, and the metal function of the catalyst cannot be fully exerted, so that the isomerization performance of the regenerated catalyst is poor.
GB1014882A discloses a process for activating a light paraffin isomerisation catalyst having a boiling point in the range of C4 to less than 204 ℃. The light alkane isomerization catalyst in the method is prepared by reacting chlorine-containing organic matters with specified structures with a catalyst containing II-V family inorganic oxides in a non-reducing atmosphere, the activity of the catalyst is gradually reduced in the light alkane hydroisomerization reaction process, and the activation method of the deactivated catalyst comprises the following steps: the hydrocarbon feed was stopped, the reaction temperature and hydrogen flow were maintained, the reaction pressure was reduced, and the catalyst was purged with pure hydrogen to restore the activity of the catalyst.
US5463166A discloses a process for activating a partially deactivated n-paraffin isomerisation catalyst comprising Pt, Cl and alumina by purging the deactivated catalyst with hydrogen at a temperature below 226.7 c for at least 1 h. The activation method is particularly suitable for being used as an intermediate step of a hydroisomerization reaction of C4-C7 normal paraffins, and can play a role in recovering the activity of the catalyst and prolonging the service life of the catalyst.
US5654247A discloses a process for activating a deactivated or partially deactivated paraffin isomerisation catalyst by activating the deactivated catalyst by suitably increasing the hydrogen/hydrocarbon ratio and reaction temperature of the isomerisation reaction and after the activation the reaction hydrogen/hydrocarbon ratio and reaction temperature are restored. The method is suitable for activating Pt-containing chlorinated alumina after inactivation in isomerization reactions of n-butane, n-pentane, n-hexane and n-heptane.
US5705731A discloses a process for activating a hydrocarbon isomerisation catalyst, which process is suitable for the activation of Pt-containing chlorided alumina catalysts after deactivation in a process for isomerising C4-C7 alkanes and/or C6-C7 cycloalkanes. The isomerization process is hydrogen, chlorides such as carbon tetrachloride or tetrachloroethylene need to be added into the raw materials, and the activation method after the catalyst is deactivated comprises two steps: a first step of increasing the hydrogen/hydrocarbon ratio under conditions where the chloride content of the feedstock is unchanged or decreased; and secondly, increasing the concentration of the chloride additive in the raw materials. However, the above method is only applicable to regeneration after deactivation of the catalyst due to adsorption of heavy hydrocarbons in the raw material on the surface of the catalyst, and cannot be applied to regeneration after deactivation of the catalyst due to destruction of the acid center of the catalyst by water in the raw material or carbon deposition.
Disclosure of Invention
The object of the present invention is to provide a regeneration method of a deactivated light paraffin isomerization catalyst, which can recover the isomerization performance of the deactivated catalyst containing Pt chlorided alumina.
The invention provides a regeneration method of a deactivated light paraffin isomerization catalyst, which comprises the following steps:
(1) and (3) decarbonizing: carrying out primary roasting on the inactivated light paraffin isomerization catalyst for 1-10 hours at 300-450 ℃ by using nitrogen with the oxygen content of 0.2-2 vol%, and then heating to 500-550 ℃ to carry out secondary roasting in the air for 2-10 hours to obtain a decarbonized catalyst;
(2) reduction: enabling hydrogen to contact with the decarbonization catalyst for reduction treatment to obtain a reduced catalyst;
(3) pre-chlorination: carrying out pre-chlorination treatment on the reduced catalyst by using hydrogen containing HCl to obtain a pre-chlorinated catalyst;
(4) chlorination: under the condition of hydrogen, AlCl is reacted3And contacting with the catalyst after the pre-chlorination treatment to perform chlorination treatment.
Through the technical scheme, the method can regenerate the deactivated Pt-containing chlorinated alumina catalyst, recover the isomerization performance of the catalyst, do not need to replace a fresh catalyst, and can effectively reduce the use cost of the catalyst.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The invention provides a regeneration method of a deactivated light paraffin isomerization catalyst, which comprises the following steps:
(1) and (3) decarbonizing: carrying out primary roasting on the inactivated light paraffin isomerization catalyst for 1-10 hours at 300-450 ℃ by using nitrogen with the oxygen content of 0.2-2 vol%, and then heating to 500-550 ℃ to carry out secondary roasting in the air for 2-10 hours to obtain a decarbonized catalyst;
(2) reduction: contacting hydrogen with a decarbonization catalyst to carry out reduction treatment to obtain a reduced catalyst;
(3) pre-chlorination: carrying out pre-chlorination treatment on the reduced catalyst by using hydrogen containing HCl to obtain a pre-chlorinated catalyst;
(4) chlorination: under the condition of hydrogen, AlCl is reacted3Contacting with the catalyst after the pre-chlorination treatment to perform chlorination treatment.
The method can regenerate the deactivated Pt-containing chlorinated alumina catalyst, recover the isomerization performance of the catalyst, do not need to replace a fresh catalyst, and can effectively reduce the use cost of the catalyst.
According to the present invention, in the step (1), the calcination can remove the carbon deposit and the adsorbed heavy hydrocarbons in the deactivated catalyst while oxidizing the active metal component of the catalyst, thereby obtaining a catalyst in which the active metal component is in an oxidized state. In one embodiment, the first stage roasting is carried out for 1-5 hours at 320-420 ℃ by using nitrogen with the oxygen content of 0.2-1.5 vol%; and roasting the mixture for the second-stage roasting for 2 to 8 hours at 500 to 540 ℃.
According to the invention, the roasting pressure can be changed in a larger range, the pressure of the first-stage roasting and the pressure of the second-stage roasting can be respectively and independently 0.1-3.0 MPa, and oxygen-containing nitrogen and inactivated light in the first-stage roastingThe volume ratio of the alkane isomerization catalyst can be 200-2000 h-1The volume ratio of air to the inactivated light paraffin isomerization catalyst in the second-stage roasting can be 200-2000 h-1。
According to the invention, the light paraffin isomerization catalyst which is not deactivated comprises a carrier and 0.05-1.0 mass%, preferably 0.05-0.5 mass% of platinum and 3.8-10.0 mass%, preferably 4.0-8.0 mass% of chlorine based on the carrier. The support is preferably alumina, more preferably gamma-alumina.
The light paraffin isomerization catalyst may be prepared by methods well known to those skilled in the art. In one embodiment, a method for preparing a light paraffin isomerization catalyst comprises: roasting the alumina carrier at 400-650 ℃, then soaking the alumina carrier with a solution containing a platinum compound, drying, roasting and reducing to obtain the alumina carrier containing platinum, and finally chlorinating the alumina carrier with a chlorine-containing compound to obtain the light alkane isomerization catalyst. The chlorine-containing compound is preferably one or more of alkyl aluminum chloride, carbon tetrachloride, chloroform, dichloromethane and aluminum trichloride, and the platinum-containing compound is preferably chloroplatinic acid.
According to the present invention, the step (2) reduces the decarbonized catalyst, and the conditions of the reduction treatment may include: the temperature is 400-650 ℃, the preferred temperature is 450-600 ℃, the time is 0.5-10 h, the preferred time is 1-6 h, the pressure is 0.1-3 MPa, the preferred pressure is 0.1-2.5 MPa, and the volume ratio of the hydrogen to the decarbonization catalyst can be 200-2000 h-1Preferably 200 to 1500 hours-1。
In one embodiment, to ensure safe transition of the processing system from an oxidizing atmosphere to a reducing atmosphere, the system to be subjected to the reduction process is subjected to gas displacement and purging with an inert gas, which may be one or more of nitrogen, helium, and argon, preferably nitrogen. The conditions for gas displacement and purging may include: the temperature is 450-550 ℃, the time is 0.5-3 hours, and the volume ratio of the scavenging gas to the calcined catalyst is 800-1500 hours-1Preferably, the oxygen content of the tail gas discharged after gas displacement and purging is less than 0.1% by volume.
According to the invention, the hydrogen used for the reduction has a purity of not less than 90% by volume, preferably 90 to 99% by volume.
According to the present invention, in order to adjust the chlorine content in the reduced catalyst, the reduced catalyst is subjected to a pre-chlorination treatment with hydrogen gas containing HCl in step (3). The HCl content of the HCl-containing hydrogen gas can vary widely, for example, from 1 to 20 vol%, preferably from 3 to 16 vol%; the conditions of the pre-chlorination treatment may include: the time is 0.5-10 h, the temperature is 400-650 ℃, preferably 450-600 ℃, the pressure is 0.1-3.0 MPa, preferably 0.1-2.5 MPa, and the volume ratio of HCl-containing hydrogen to the catalyst after reduction treatment is 200-2000 h-1Preferably 200 to 1500 hours-1。
According to the invention, step (4) is carried out with AlCl3The catalyst after the pre-chlorination is further chlorinated to reach the required chlorine content. The conditions of the chlorination treatment may include: the temperature is 400-650 ℃, the preferred temperature is 450-600 ℃, the pressure is 0.1-3.0 MPa, the preferred pressure is 0.1-1.0 MPa, the time is 0.1-10 h, the preferred time is 0.2-6 h, and AlCl3The mass ratio of the catalyst to the catalyst after the pre-chlorination treatment is (10-50): 100. preferably (10-40): 100.
in one embodiment, gaseous AlCl is carried with hydrogen as a carrier gas3Dispersing in carrier gas, and contacting with catalyst after pre-chlorination treatment to make chlorination treatment. Preferably, AlCl3Heating to sublimation temperature above 178 deg.C, and carrying sublimed AlCl with hydrogen as carrier gas3The steam contacts with the catalyst after the pre-chlorination treatment to carry out chlorination treatment.
According to the invention, the volume ratio of the carrier gas to the catalyst after the pre-chlorination treatment can be changed in a large range, for example, 100-5000 h-1Preferably 200 to 2000h-1。
In one embodiment, after the chlorination process is completed, the catalyst is purged with hydrogen to reduce the temperature to below 50 ℃.
According to the present invention, the deactivated light paraffin isomerization catalyst comprises an alumina support, platinum in an amount of 0.05 to 1.0 mass%, preferably 0.05 to 0.5 mass%, based on the alumina support, chlorine in an amount of 3.8 to 10.0 mass%, preferably 4.0 to 8.0 mass%, and carbon in an amount of 0.1 to 3.0 mass%, based on the alumina support.
The invention is further illustrated by the following examples, but is not to be construed as being limited thereto.
The Pt content of the catalysts in the examples and the comparative examples is measured by an Shimadzu UV2401PC ultraviolet-visible spectrophotometer, the sample is firstly dissolved by hydrochloric acid, and then is complexed by stannous chloride, and the Pt content is measured by a colorimetric method.
The Cl content of the catalyst is measured by adopting a Switzerland Vanton potentiometric titrator 905, a sample is firstly dissolved by NaOH, chloride ions are extracted, and then silver nitrate is used for titration to measure the Cl content.
The carbon content of the catalyst is determined by a CS-444 sulfur-carbon instrument from Leco company, and the sample is crushed, dried and burnt at the high temperature of more than 1000 ℃ to generate CO by high-frequency induction2And measuring the carbon content by using infrared absorption spectrum.
Example 1
This example uses the process of the present invention to regenerate the deactivated light paraffin isomerization catalyst after the reaction evaluation.
The fresh isomerization catalyst a contained 0.25 mass% of Pt and 5.90 mass% of Cl, based on the alumina carrier, using γ -alumina as a carrier.
60.0g of a fresh isomerization catalyst A was taken and put into a medium-sized evaluation apparatus of a C5/C6 isomerization catalyst, and the catalyst was evaluated using a mixed hydrocarbon containing 50 mass% of n-pentane and 50 mass% of n-hexane as a raw material under the conditions: the reaction temperature is 170 ℃, the reaction pressure is 3.3MPa, and the feeding mass space velocity is 4.0h-1Hydrogen/hydrocarbon molar ratio 0.2, reaction time 800 h. Stopping feeding after the reaction is finished, reducing the pressure of the reactor to 0.1MPa, purging the catalyst for 1h at the constant temperature of 130 ℃ by using hydrogen, wherein the volume ratio of the hydrogen to the catalyst is 800h-1Continue to communicate H2Cooling to below 50 deg.C, discharging under the protection of nitrogen gas to obtain deactivated light paraffin isomerization catalyst B, storing in anhydrous and oxygen-free environment, and deactivating light paraffin isomerization catalyst BThe results of the carbon content, Cl content and Pt content analyses are shown in Table 1.
10.0g of the deactivated light paraffin isomerization catalyst B is placed in a fixed bed reactor for regeneration, and the specific steps are as follows:
(1) and (3) decarbonizing: introducing nitrogen with the oxygen content of 0.5 volume percent into the reactor, wherein the pressure is 0.3MPa, and the volume ratio of the oxygen-containing nitrogen to the inactivated light alkane isomerization catalyst B is 800h-1Heating to 400 ℃ at a heating rate of 50 ℃/h for first-stage constant-temperature roasting for 3h until the oxygen content of gas at the outlet and the inlet of the reactor is the same, introducing air instead, wherein the pressure is 0.3MPa, and the volume ratio of the air to the inactivated light alkane isomerization catalyst B is 800h-1And simultaneously, gradually raising the temperature of the reactor to 510 ℃ at the heating rate of 50 ℃/h, and carrying out two-stage constant-temperature roasting for 4h at 510 ℃ to obtain the decarburized catalyst, wherein the decarburized catalyst does not contain carbon and the chlorine content is 1.05 mass percent.
(2) Reduction: purging the calcined decarbonized catalyst for 1h by using nitrogen, replacing oxygen in a reaction system, simultaneously cooling to 500 ℃, and enabling the volume ratio of the nitrogen for purging to the calcined decarbonized catalyst to be 1000h-1Stopping nitrogen purging when the oxygen content in the tail gas discharged from the outlet of the reactor is lower than 0.1 volume percent, introducing hydrogen (with the purity of 99 volume percent) into the reactor for reduction treatment for 4 hours under the conditions of 500 ℃, 0.3MPa and the volume ratio of the hydrogen to the decarbonization catalyst of 800 hours-1Obtaining the catalyst after reduction treatment;
(3) pre-chlorination: the reduced catalyst is pre-chlorinated for 2h by hydrogen containing 10 volume percent of hydrogen chloride under the conditions of 530 ℃, 0.3MPa and the volume ratio of the hydrogen containing the hydrogen chloride to the reduced catalyst of 1000h-1Obtaining a catalyst after pre-chlorination treatment;
(4) chlorination: using sublimed AlCl to carry the catalyst after the pre-chlorination treatment3Chloridizing with steam hydrogen for 1h, and using AlCl3The dosage of the catalyst is 2.4g, the chlorination condition is 520 ℃, the pressure is 0.2MPa, and the volume ratio of hydrogen to the catalyst after the pre-chlorination treatment is 600h-1After the chlorination treatment, continuously introducing hydrogen gas to reduce the temperature to below 50 ℃ to prepare a regenerated catalyst C, and introducing the regenerated catalyst C into nitrogen gasDischarging under protection, and storing in anhydrous and oxygen-free environment.
The results of analyzing the carbon content, chlorine content and platinum content of the regenerated catalyst C are shown in Table 1. It can be seen from the table that after regeneration of the catalyst, carbon is removed, the platinum content remains unchanged and the chlorine content is close to that of the fresh catalyst.
Example 2
The deactivated light paraffin isomerization catalyst B was regenerated as in example 1, except that in step (3), the reduced catalyst was prechlorinated with hydrogen containing 15 vol% HCl at a pressure of 1.1MPa under otherwise unchanged conditions, and a regenerated catalyst D was finally obtained.
The results of analyzing the carbon content, chlorine content and platinum content of the regenerated catalyst D are shown in Table 1.
Example 3
The deactivated light paraffin isomerization catalyst B was regenerated in the same manner as in example 1 except that the temperature of the preliminary chlorination in step (3) was 400 ℃ and the pressure was 2.0MPa, and the other conditions were not changed, to finally obtain regenerated catalyst E.
The results of analyzing the carbon content, chlorine content and platinum content of the regenerated catalyst E are shown in Table 1.
Example 4
The deactivated light paraffin isomerization catalyst B was regenerated as in example 1, except that in step (3), the reduced catalyst was preshlorinated with hydrogen containing 5 vol% HCl at a temperature of 650 ℃ under otherwise unchanged conditions, to finally obtain regenerated catalyst F.
The results of analyzing the carbon content, chlorine content and platinum content of the regenerated catalyst F are shown in Table 1.
Example 5
This example uses the process of the present invention to regenerate an industrially deactivated light paraffin isomerization catalyst.
The fresh industrial light paraffin isomerization catalyst G contained 0.25 mass% of Pt and 5.71 mass% of Cl, based on the γ -alumina as a carrier and the alumina carrier. Catalyst G deactivated after 5 years of operation of the industrial unit under the following operating conditions: temperature of 130-170 deg.CThe pressure is 3.3MPa, and the light alkane feeding mass space velocity is 1.0h-1The hydrogen/hydrocarbon molar ratio was 0.2, and the light paraffin feedstock contained 4.84 mass% of C4 paraffin, 41.29 mass% of C5 paraffin, 50.26 mass% of C6 paraffin, 1.12 mass% of benzene, and 2.49 mass% of C7 +(carbon number is not less than 7) hydrocarbons. The deactivated industrial light paraffin isomerization catalyst H contained 0.25 mass% of Pt, 4.68 mass% of Cl, and 0.87 mass% of carbon.
20.0g of deactivated technical light paraffin isomerization catalyst H was placed in a fixed bed reactor and regenerated as in example 1 except that AlCl used in the chlorination treatment of step (4)34.0g, regenerated catalyst I was obtained. The results of analyzing the carbon content, chlorine content and platinum content of the regenerated catalyst I are shown in Table 1. As can be seen from the table, after the deactivated catalyst was regenerated, carbon was completely removed, the platinum content remained unchanged, and the Cl content was close to that of the fresh catalyst.
Comparative example 1
The deactivated light paraffin isomerization catalyst B was regenerated as in example 1, except that the step (1) was omitted, and the deactivated light paraffin isomerization catalyst B was subjected to reduction with hydrogen, pre-chlorination with hydrogen containing 10 vol% HCl, and then to chlorination to obtain regenerated catalyst J, which was discharged under nitrogen protection and stored in an anhydrous and oxygen-free environment.
The results of analyzing the carbon content, chlorine content and platinum content of the regenerated catalyst J are shown in Table 1. As can be seen from the table, the carbon content in regenerated catalyst J is essentially equivalent to that of deactivated light paraffin isomerization catalyst B.
Comparative example 2
The deactivated light paraffin isomerization catalyst B was regenerated as in example 1, except that step (2) was omitted, the decarbonized catalyst was first pre-chlorinated with hydrogen containing 10 vol% HCl and then chlorinated to obtain regenerated catalyst K, which was discharged under nitrogen protection and stored in an anhydrous and oxygen-free environment.
The results of analyzing the carbon content, chlorine content and platinum content of the regenerated catalyst K are shown in Table 1. As can be seen from the table, the regenerated catalyst K, although essentially free of carbon, had a lower Cl content than the fresh catalyst.
Comparative example 3
The deactivated light alkane isomerization catalyst B was regenerated as in example 1, except that the step (3) was omitted, and the reduced catalyst obtained after the hydrogen treatment was directly chlorinated to obtain a regenerated catalyst L, which was discharged under the protection of nitrogen and stored in an anhydrous and oxygen-free environment.
The results of analyzing the carbon content, chlorine content and platinum content of the regenerated catalyst L are shown in Table 1. It can be seen from the table that the regenerated catalyst L, although essentially free of carbon, has a lower Cl content than the fresh catalyst.
Comparative example 4
The deactivated light alkane isomerization catalyst B was regenerated as in example 1 except that step (4) was omitted and the regenerated catalyst M was obtained and discharged under nitrogen and stored in a water-free and oxygen-free environment.
The results of analyzing the carbon content, chlorine content and platinum content of the regenerated catalyst M are shown in Table 1. It can be seen from the table that the regenerated catalyst M, although essentially free of carbon, has a much lower Cl content than the fresh catalyst.
Comparative example 5
20.0g of deactivated light paraffin isomerization catalyst B was charged to a quartz tube reactor and regenerated according to the method of patent GB 969863A.
The method comprises the following specific steps:
(1) treating the deactivated light alkane catalyst B in an air flow, wherein the volume ratio of air to catalyst is 500h-1The pressure is 0.1MPa, in order to prevent temperature runaway, the temperature of a catalyst bed layer is raised step by heating from 130 ℃ to 204 ℃ within 3.75h, then from 204 ℃ to 230 ℃ within 1h, then from 230 ℃ to 260 ℃ within 1h, then from 260 ℃ to 480 ℃ within 4.25h, the temperature is raised to 480 ℃ within 480 ℃ for treatment at constant temperature for 1h, and then the temperature is continuously lowered to 285 ℃ by blowing;
(2) after the air treatment is finished and the catalyst bed layer is stabilized to 285 ℃, a feeding pump is started to inject CCl into the carrier gas at a constant speed4By containing CCl4The catalyst is subjected to chlorination treatment for 1h, and the volume ratio of the air to the catalyst in the treatment process is 500h-1，CCl4The injection amount was 6.5g, and the introduction of CCl was stopped after the chlorination treatment was completed4And blowing air to raise the temperature, raising the temperature of the catalyst bed to 480 ℃ for 4 hours, treating at 480 ℃ for 1 hour at constant temperature, then reducing the temperature to 130 ℃ to obtain a regenerated catalyst N, discharging under the protection of nitrogen, and storing in an anhydrous and oxygen-free environment.
The results of analyzing the carbon content, chlorine content and platinum content of the regenerated catalyst N are shown in Table 1. As can be seen from the table, the regenerated catalyst N, although substantially free of carbon, had a lower Pt content than the fresh catalyst.
Example 6
The following examples examine the C5/C6 isomerization performance of each catalyst.
A mixed hydrocarbon containing 20 mass% of n-pentane and 80 mass% of n-hexane was used as a raw material, and a fresh catalyst, a deactivated catalyst and a regenerated catalyst were evaluated on a small fixed bed reactor under the following conditions: the reaction temperature is 130 ℃, the reaction pressure is 3.3MPa, and the feeding mass space velocity is 1.5h-1The hydrogen/hydrocarbon molar ratio was 0.5, the reaction time was 10 hours, and the results are shown in Table 1, taking the average reaction result of 10 hours.
In the table, the number of the first and second,
c5 isomerization rate ═ mass of isopentane in product/mass of C5 paraffins in product x 100%;
c6 isomerization rate ═ 1- (mass of n-hexane in product/mass of C6 paraffin in product)) × 100%;
selectivity to C6 ═ 100% (mass of 2, 2-dimethylbutane in product/mass of C6 alkanes in product).
TABLE 1
As can be seen from Table 1, the process of the present invention can effectively restore the performance of the deactivated light paraffin isomerization catalyst, and the obtained regenerated catalyst has higher isomerization rate of C5, isomerization rate of C6 and selectivity of C6 than the regenerated catalyst obtained by the comparative process.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (10)
1. A method for regenerating a deactivated light paraffin isomerization catalyst, comprising the steps of:
(1) and (3) decarbonizing: carrying out primary roasting on the inactivated light paraffin isomerization catalyst for 1-10 hours at 300-450 ℃ by using nitrogen with the oxygen content of 0.2-2 vol%, and then heating to 500-550 ℃ to carry out secondary roasting in the air for 2-10 hours to obtain a decarbonized catalyst;
(2) reduction: enabling hydrogen to contact with the decarbonization catalyst for reduction treatment to obtain a reduced catalyst;
(3) pre-chlorination: carrying out pre-chlorination treatment on the reduced catalyst by using hydrogen containing HCl to obtain a pre-chlorinated catalyst;
(4) chlorination: under the condition of hydrogen, AlCl is reacted3And contacting with the catalyst after the pre-chlorination treatment to perform chlorination treatment.
2. The method as claimed in claim 1, wherein, in the step (1), the first stage roasting is carried out for 1 to 5 hours at 320 to 420 ℃ with nitrogen gas having an oxygen content of 0.2 to 1.5 vol%.
3. The method as claimed in claim 1, wherein, in the step (1), the secondary roasting is carried out for 2 to 8 hours at 500 to 540 ℃ by using air.
4. The method according to claim 1, wherein in the step (1), the pressure of the primary roasting and the secondary roasting is 0.1-3.0 MPa independently, and the volume ratio of the oxygen-containing nitrogen gas to the deactivated light paraffin isomerization catalyst in the primary roasting is 200-2000 h-1The volume ratio of the air to the inactivated light paraffin isomerization catalyst in the second-stage roasting is 200-2000 h-1。
5. The method according to claim 1, wherein in step (2), the conditions of the reduction treatment include: the temperature is 400-650 ℃, the time is 0.5-10 h, the pressure is 0.1-3.0 MPa, and the volume ratio of the hydrogen to the calcined catalyst is 200-2000 h-1。
6. The method according to claim 1, wherein in the step (2), the hydrogen purity is not less than 90 vol%.
7. The method according to claim 1, wherein in the step (3), the HCl content in the HCl-containing hydrogen gas is 1-20 vol%;
the conditions of the pre-chlorination treatment comprise: the time is 0.5-10 h, the temperature is 400-650 ℃, the pressure is 0.1-3.0 MPa, and the volume ratio of the HCl-containing hydrogen to the reduced catalyst is 200-2000 h-1。
8. The method according to claim 1, wherein in the step (4), the chlorination treatment conditions include: the temperature is 400-650 ℃, the pressure is 0.1-3.0 MPa, the time is 0.1-10 h, and the AlCl is3The mass ratio of the catalyst to the catalyst after the pre-chlorination treatment is (10-50): 100.
9. the method of claim 1, wherein the gaseous AlCl is introduced into the reactor in step (4) using hydrogen as a carrier gas3Dispersing the catalyst in the carrier gas, and contacting the catalyst after the pre-chlorination treatment to perform the chlorination treatment;
the volume ratio of the carrier gas to the catalyst after the pre-chlorination treatment is 200-2000 h-1。
10. The method according to any one of claims 1 to 9, wherein the deactivated light paraffin isomerization catalyst comprises an alumina support, platinum in an amount of 0.05 to 1.0 mass% and chlorine in an amount of 3.8 to 10.0 mass% based on the alumina support, and carbon in an amount of 0.1 to 3.0 mass% based on the alumina support.
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