CN102151589B - In-situ regeneration method for molecular sieve catalyst - Google Patents
In-situ regeneration method for molecular sieve catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 79
- 238000011069 regeneration method Methods 0.000 title claims abstract description 46
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 26
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 15
- 238000010926 purge Methods 0.000 claims abstract description 65
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 46
- 230000008929 regeneration Effects 0.000 claims abstract description 38
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000011259 mixed solution Substances 0.000 claims abstract description 25
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 23
- 239000000203 mixture Substances 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000007800 oxidant agent Substances 0.000 claims abstract description 13
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 239000007789 gas Substances 0.000 claims abstract description 8
- 239000000376 reactant Substances 0.000 claims abstract description 7
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 6
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 25
- 230000001172 regenerating effect Effects 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 15
- 230000002779 inactivation Effects 0.000 claims description 13
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 10
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 claims description 8
- 150000004996 alkyl benzenes Chemical class 0.000 claims description 8
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 7
- 150000001336 alkenes Chemical class 0.000 claims description 6
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 5
- 235000019253 formic acid Nutrition 0.000 claims description 5
- 238000011084 recovery Methods 0.000 claims description 5
- SCKXCAADGDQQCS-UHFFFAOYSA-N Performic acid Chemical compound OOC=O SCKXCAADGDQQCS-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 239000005416 organic matter Substances 0.000 claims description 4
- 238000007790 scraping Methods 0.000 claims description 4
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 claims description 3
- -1 tertbutanol peroxide Chemical class 0.000 claims description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N tert-butyl alcohol Substances CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 abstract description 3
- 150000002978 peroxides Chemical class 0.000 abstract 1
- 230000001502 supplementing effect Effects 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 description 12
- 230000000694 effects Effects 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 230000008569 process Effects 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 7
- 229960002163 hydrogen peroxide Drugs 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 230000009849 deactivation Effects 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 229910004339 Ti-Si Inorganic materials 0.000 description 4
- 229910010978 Ti—Si Inorganic materials 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000004939 coking Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000006735 epoxidation reaction Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000009418 renovation Methods 0.000 description 2
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- CUDYYMUUJHLCGZ-UHFFFAOYSA-N 2-(2-methoxypropoxy)propan-1-ol Chemical compound COC(C)COC(C)CO CUDYYMUUJHLCGZ-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005235 decoking Methods 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012913 prioritisation Methods 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 239000006200 vaporizer Substances 0.000 description 1
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- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses an in-situ regeneration method for a molecular sieve catalyst, which is characterized by comprising the following technology steps of: (1) purging the inactivated molecular sieve catalyst by using a mixture of air, nitrogen and light hydrocarbons to remove a reactant; (2) after the gas purging, purging by using vapor of a mixture of water, methanol, ethanol and propanol; (3) supplementing nitrogen until a regeneration pressure reaches 0.5-5 MPa; adding into a regeneration mixed solution, wherein an oxidizing substance in the mixed solution is peroxide, a solvent is a mixture of alcohol and water, a regeneration temperature is 30-140 DEG C, a mass airspeed is 0.5-5 h<-1>, and a regeneration time is 2-20 hours; (4) purging the regenerated molecular sieve catalyst by using vapor of a mixture of water and alcohol; and (5) after the vapor purging is completed, purging by using mixture of air and hydrocarbons.
Description
Technical field
The present invention relates to catalysis technical field; In situ regeneration method for a kind of molecular sieve catalyst; More particularly, the present invention relates to a kind of in situ regeneration method that is applicable to slight decaying catalyst, specifically refer to the oxidation reaction that Ti-Si catalyst relates to; The alkylated reaction of reformation arene engaging scraping alkene, the course of reaction of the synthetic reaction of long-chain alkyl benzene and little molecular alkyl benzene.
Background technology
Loss is active gradually after operation a period of time for the molecular sieve catalyst that the oil-refining chemical process is used, and plug-hole causes in microporous molecular sieve owing to accessory substance accumulates in for this.This type of accessory substance generally roughly divides two kinds, and the one, the big molecular product that generates receives the duct diffusion effect and can't spread out, and the 2nd, continue the carbon deposit that charing forms graphite mould.For second kind of accessory substance carbon deposit, through the regeneration of oxidation burn off, activity can partially or completely be restored, and in commercial production, still can continue to use.The catalyst that has even the use of can repeatedly regenerating have reached energy savings, increase the purpose of benefit.
During coking deactivation catalyst coke-burning regeneration, carbon deposit will react with oxygen and be removed, and produce a large amount of heat simultaneously.If heat release too much or too concentrated, atmosphere can't be taken away the heat that produces, and will cause the mistake thermal response of catalyst, causes catalyst property to change, and like the enrichment of carried metal the character of catalyst is caused negative effect.This kind renovation process molecular sieve catalyst needs before regeneration through high dry, then needs long-time cooling after the high-temperature roasting, needs to consume significant amount of energy and takies equipment.To be most coke-burning regeneration process need shift out reaction system with catalyst to the another one important problem carries out device and regenerate outward, consumes and strengthen.
In existing relevant coking deactivation catalyst regeneration patent, most of patents consider emphatically how to prevent that decaying catalyst from concentrating or the problem of excessive exotherms in regenerative process.Like US 5,037,785 suggestions are under oxygen containing gas, and the method that adopts laser radiation is to the catalyst decoking; US 4,202, and 865 suggestions are annotated oxygen with batch (-type), and US 4; 780,195 think then that with US 4,417,975 grades adding a certain amount of water prevents sintering of catalyst etc. in atmosphere.The patent of the relevant too much problem of heat release through the coking deactivation catalyst treatment being solved decaying catalyst when regeneration is then rare.
In a lot of molecular sieve catalytics reactions, it is inviolent that reaction is carried out, the reaction that relates to like Ti-Si catalyst; The reaction of reformation arene engaging scraping alkene; In the course of reaction of the synthetic reaction of long-chain alkyl benzene and little molecular alkyl benzene, the common feature of this type reaction is that reaction condition comparatively relaxes, and accessory substance is different with the graphite mould carbon deposit mostly; They with catalyst combine and insecure; Can realize the basic recovery of catalyst activity through means such as cleaning, immersion, displacements, and operate fairly simplely that energy consumption is lower.
Patent CN 1768956A thinks that the carbon deposit on the catalyst can be through the distinct methods processing to obtain better result, and the temperature when helping controlling its regeneration reduces the influence of high temperature to catalyst performance, improves the activity of regenerated catalyst.Its processing mode is to add organic solvents such as carbon deposit cleaner such as propylene glycol methyl ether acetate, propylene-glycol ethyl ether, dipropylene glycol methyl ether, propylene glycol monomethyl ether earlier decaying catalyst is carried out washing by soaking.But this method solvent load is excessive, and the big molecule accessory substance in the washing agent also is difficult to separate.
Patent US 5,916, and 835 pairs of heterogeneous decaying catalysts of titaniferous that are used for epoxidation of ethylene adopt materials such as water, alcohol, ester, nitrile, ether, aromatic hydrocarbons, ketone to handle, and have reached the purpose of recovering catalyst activity.The Ti-Si catalyst that this patent is related, in the epoxidation of ethylene process, generate in the ethylene oligomerization course of reaction two, trimer or generate two, two polyethers with oxide.Because their molecule is bigger, the diffusion rate in the catalyst duct is slower, is prone to block the duct, and reactant can't be arrived on the active sites, causes catalyst activity reduction.Used catalyst is handled through materials such as moisture, pure, ester, nitrile, ether, aromatic hydrocarbons, ketone, and most of activity of catalyst is restored.
Patent CN 101439299A handles the titanium-silicon molecular sieve catalysts of inactivation under 40～120 ℃ with the mixed solution of a kind of hydrogen peroxide solution and formic acid; The quality proportioning of hydrogen peroxide and organic acid compound is 1～8: 1; This method requires reaction to be liquid phase; And the concentration of hydrogen peroxide is higher, at high temperature uses to have more difficulty.
Above-mentioned several method all need shift out catalyst from reaction system, increased consumption, and need join immersion system in addition, realizes comparatively difficulty.
Summary of the invention
The objective of the invention is basis, a kind of in situ regeneration method that is directed against the molecular sieve catalyst of inactivation in the slight catalytic reaction of better effects if is provided based on the difference and the prior art of different catalysts deactivation mechanism.
The present invention is a kind of in situ regeneration method of molecular sieve catalyst, it is characterized in that:
With the catalyst of inactivation with a kind of mixed solution 30～140 ℃ of following in-situ treatment, described mixed solution is to contain the aqueous solution of oxidizing substance and the mixture of one or more organic matter solvents;
Processing step comprises:
(1) molecular sieve catalyst of inactivation is purged with one or more mixture of air, nitrogen, light hydrocarbons remove reactant, the gas purging temperature is 50～350 ℃, and volume space velocity is 200～2000h
-1, purge time is 0.5～5h;
(2) behind the gas purging, switch wherein one or more mixture purge vapor of water, methyl alcohol, ethanol, propyl alcohol, the purge vapor temperature is 70～150 ℃, and mass space velocity is 0.5～5h
-1, purge time is 2～20h;
(3) after purge vapor finishes; Mending nitrogen to regeneration pressure is 0.5～5MPa, squeezes into regenerative mixed solution, and oxidizing substance can be tertbutanol peroxide, Peracetic acid, peroxyformic acid, hydrogen peroxide in the mixed solution; Solvent can be the mixture of wherein one or more and the water of methyl alcohol, ethanol, propyl alcohol, formic acid; It is 5～20% that oxidizing substance accounts for the mixed solution mass percent, and regeneration temperature is 30～140 ℃, and mass space velocity is 0.5～5h
-1, the recovery time is 2～20h;
(4) molecular sieve catalyst after will regenerating switches wherein one or more mixture purge vapor of water, methyl alcohol, ethanol, propyl alcohol, and the purge vapor temperature is 70～150 ℃, and mass space velocity is 0.5～5h
-1, purge time is 2～20h;
(5) after purge vapor finished, one or more the mixture that switches air, nitrogen, light hydrocarbons purged, and purging temperature is 50～350 ℃, and volume space velocity is 200～2000h
-1, purge time is 0.5～5h;
According to in-situ regeneration processing step of the present invention, its preferred version is characterised in that:
With the catalyst of inactivation with a kind of mixed solution 80～120 ℃ of following in-situ treatment, described mixed solution is to contain the aqueous solution of oxidizing substance and the mixture of one or more organic matter solvents;
Processing step comprises:
(1) molecular sieve catalyst with inactivation removes reactant with air or nitrogen purging, and purging temperature is 120～170 ℃, and volume space velocity is 300～600h
-1, purge time is 1～3h;
(2) behind the gas purging, switch steam purging, the steam purging temperature is 120～150 ℃, and mass space velocity is 1～3h
-1, purge time is 4～8h;
(3) after steam purging finishes; Mending nitrogen to regeneration pressure is 1～2MPa, squeezes into regenerative mixed solution, and oxidizing substance can be Peracetic acid, peroxyformic acid, hydrogen peroxide in the mixed solution; Solvent can be the mixture of wherein one or both and the water of methyl alcohol, ethanol; It is 10～15% that oxidizing substance accounts for the mixed solution mass percent, and regeneration temperature is 80～120 ℃, and mass space velocity is 1～3h
-1, the recovery time is 4～8h;
(4) molecular sieve catalyst after will regenerating feeds steam purging, and the steam purging temperature is 120～150 ℃, and mass space velocity is 1～3h
-1, purge time is 4～8h;
(5) after purge vapor finishes, switch nitrogen and purge, it is 120～170 ℃ that nitrogen purges temperature, and volume space velocity is 300～600h
-1, purge time is 3～5h;
In the renovation process provided by the invention; Handled deactivated molecular sieve catalyst; Mainly be meant the reaction that Ti-Si catalyst relates to, comprise the titanium-silicon molecular sieve catalyst that uses in the course of reaction of synthetic reaction and little molecular alkyl benzene of reaction, long-chain alkyl benzene of reformation arene engaging scraping alkene.
Method provided by the invention adopts hydrogenperoxide steam generator to clean the catalyst of inactivation, has good carbon removal effect, and need not to carry out high-temperature roasting after the washing and just can realize good regeneration effect.Compared with prior art; First, five liang of step also is necessary in the high temperature regeneration technology outside device in time in its preferred version, and the purpose in second, four liang of step is to reclaim to be adsorbed on reactant and the cleaning agent in the molecular sieve pore passage, reduces production costs; The 3rd step was core procedure of the present invention; Advantage simple to operate, efficient energy-saving that the whole operation process has, under the regenerated from washing condition of optimum, the carbon residue content of regenerative agent is near the regeneration effect of high-temperature roasting.
The specific embodiment
Among Comparative Examples and the embodiment, the oil-off olefin catalyst is as process object at the bottom of the employing reformation aromatic hydrocarbons tower, and as the regeneration evaluation index, industrial deactivator C% is 1.73% with the C% in the catalyst.
What need to specify is, behind catalysqt deactivation, does not and then carry out in-situ regeneration among Comparative Examples and the embodiment, but the catalyst that adopts industrial inactivation as a reference.This is because catalyst life is longer, and lab scale catalysqt deactivation process is difficult to duplicate, and is difficult to relatively implement selected prioritization scheme.Following embodiment does not influence the protection of claims of the present invention to molecular sieve catalyst in-situ regeneration process program.
Comparative Examples 1
10g decaying catalyst device is outer handles 2h through 110 ℃, and 1h are handled in temperature programming to 200 ℃ then, 300 ℃, 400 ℃, handle 4h for 550 ℃, and analyzing regenerative agent C% is 0.19%.Regeneration rear catalyst called after D1.
Comparative Examples 2
The 5g deactivator; 65 ℃ of washings of 50g methyl alcohol are after 30 minutes; Spent deionised water 30 minutes; Adopt formic acid, hydrogen peroxide (30wt%) mixed solution 50g (hydrogen peroxide: the formic acid mass ratio is 4: 1) 80 ℃ of washing 8h in there-necked flask of preparation, slowly drip the mode charging, analyzing regenerative agent C% is 0.37%.Regeneration rear catalyst called after D2.
Comparative Examples 3
Get the 5g decaying catalyst and pack in the reactor, rise to 150 ℃, feed nitrogen and purge 1h, nitrogen flow rate is 100ml/min.Deionized water is purged 4h through pumping into after measuring in the vaporizer gasification back feeding reactor, and the vapor quality air speed is 3h
-1Switch to high pure nitrogen and purge 4h, analyzing regenerative agent C% is 0.69%.Regeneration rear catalyst called after D3.
Embodiment 1
With Comparative Examples 3, just after steam purging is intact, be cooled to 80 ℃, pump into by 30% the industrial hydrogen peroxide solution and the mixed solution of methyl alcohol, the ratio of first alcohol and water is 1: 1 in the solvent, mass space velocity is 3h
-1, the processing time is 5 hours.Switching the steam step after regeneration finishes repeats once.Analyzing regenerative agent C% is 0.49%.Regeneration rear catalyst called after C1.
Embodiment 2
With embodiment 1, just the hydrogen peroxide solution treatment temperature is 110 ℃.Analyzing regenerative agent C% is 0.43%.Regeneration rear catalyst called after C2.
Embodiment 3
With embodiment 1, just the hydrogen peroxide solution treatment temperature is 120 ℃.Analyzing regenerative agent C% is 0.42%.Regeneration rear catalyst called after C3.
Embodiment 4
With embodiment 3, feed nitrogen before just hydrogen peroxide solution is handled, pressure rises to 0.5MPa.Analyzing regenerative agent C% is 0.40%.Regeneration rear catalyst called after C4.
Embodiment 5
With embodiment 3, feed nitrogen before just hydrogen peroxide solution is handled, pressure rises to 1.0MPa.Analyzing regenerative agent C% is 0.39%.Regeneration rear catalyst called after C5.
Embodiment 6
With embodiment 3, feed nitrogen before just hydrogen peroxide solution is handled, pressure rises to 1.5MPa.Analyzing regenerative agent C% is 0.35%.Regeneration rear catalyst called after C6.
Embodiment 7
With embodiment 3, feed nitrogen before just hydrogen peroxide solution is handled, pressure rises to 2.0MPa.Analyzing regenerative agent C% is 0.31%.Regeneration rear catalyst called after C7.
Application examples
Catalyst to after the regeneration is investigated, and reaction condition is following: feedstock oil is oil at the bottom of the reformation tower, and bromine index is 863.7mgBr/100g; 170 ℃ of reaction temperatures, reaction pressure 1.2MPa, weight space velocity 10h
-1
Table 1 catalyst removal alkene ability examination (mgBr/100g)
| Time (h) | 15 | 24 | 39 | 48 | 63 | 78 |
| Fresh dose | 21.1 | 18.7 | 21.9 | 41.9 | 56.8 | 313.6 |
| ?D1 | 19.1 | 16.2 | 21.3 | 61.3 | 106.8 | 431.8 |
| ?D2 | 23.3 | 34.5 | 47.6 | 99.1 | 157.9 | 443.1(a) |
| ?D3 | 36.2 | 32.3 | 62.6 | 147.8 | 391.2 | / |
| ?C1 | 33.1 | 37.1 | 53.5 | 93.7 | 233.7 | 576.4(a) |
| ?C2 | 31.6 | 27.9 | 42.6 | 89.1 | 212.1 | 349.1(a) |
| ?C3 | 29.1 | 31.4 | 39.5 | 75.3 | 207.1 | 317.8(a) |
| ?C4 | 34.5 | 32.7 | 45.3 | 84.2 | 214.2 | 321.3(a) |
| ?C5 | 31.5 | 39.7 | 57.4 | 101.3 | 194.8 | 544.5 |
| ?C6 | 26.3 | 24.9 | 37.8 | 79.7 | 157.6 | 482.9 |
| ?C7 | 27.1 | 21.9 | 44.2 | 71.7 | 149.8 | 471.5 |
Annotate: it is 72 hours that a represents monitoring time.
Claims (2)
1. the in situ regeneration method of a molecular sieve catalyst is characterized in that:
With the catalyst of inactivation with a kind of mixed solution 30～140 ℃ of following in-situ treatment, described mixed solution is to contain the aqueous solution of oxidizing substance and the mixture of one or more organic matter solvents;
Processing step comprises:
1) molecular sieve catalyst of inactivation is purged with one or more mixture of air, nitrogen, light hydrocarbons remove reactant, the gas purging temperature is 50～350 ℃, and volume space velocity is 200～2000h
-1, purge time is 0.5～5h;
2) behind the gas purging, switch wherein one or more mixture purge vapor of water, methyl alcohol, ethanol, propyl alcohol, the purge vapor temperature is 70～150 ℃, and mass space velocity is 0.5～5h
-1, purge time is 2～20h;
3) after purge vapor finishes; Mending nitrogen to regeneration pressure is 0.5～5MPa, squeezes into regenerative mixed solution, and oxidizing substance is tertbutanol peroxide, Peracetic acid, peroxyformic acid, hydrogen peroxide in the mixed solution; Solvent is the mixture of wherein one or more and the water of methyl alcohol, ethanol, propyl alcohol, formic acid; It is 5～20% that oxidizing substance accounts for the mixed solution mass percent, and regeneration temperature is 30～140 ℃, and mass space velocity is 0.5～5h
-1, the recovery time is 2～20h;
4) molecular sieve catalyst after will regenerating switches wherein one or more mixture purge vapor of water, methyl alcohol, ethanol, propyl alcohol, and the purge vapor temperature is 70～150 ℃, and mass space velocity is 0.5～5h
-1, purge time is 2～20h;
5) after purge vapor finished, one or more the mixture that switches air, nitrogen, light hydrocarbons purged, and purging temperature is 50～350 ℃, and volume space velocity is 200～2000h
-1, purge time is 0.5～5h;
The molecular sieve catalyst of described inactivation comprises the titanium-silicon molecular sieve catalyst that uses in the course of reaction of synthetic reaction and little molecular alkyl benzene of reaction, long-chain alkyl benzene of reformation arene engaging scraping alkene.
2. according to the described method of claim 1, it is characterized in that:
With the catalyst of inactivation with a kind of mixed solution 80～120 ℃ of following in-situ treatment, described mixed solution is to contain the aqueous solution of oxidizing substance and the mixture of one or more organic matter solvents;
Processing step comprises:
1) molecular sieve catalyst with inactivation removes reactant with air or nitrogen purging, and purging temperature is 120～170 ℃, and volume space velocity is 300～600h
-1, purge time is 1～3h;
2) behind the gas purging, switch steam purging, the steam purging temperature is 120～150 ℃, and mass space velocity is 1～3h
-1, purge time is 4～8h;
3) after steam purging finishes; Mending nitrogen to regeneration pressure is 1～2MPa, squeezes into regenerative mixed solution, and oxidizing substance is Peracetic acid, peroxyformic acid, hydrogen peroxide in the mixed solution; Solvent is the mixture of wherein one or both and the water of methyl alcohol, ethanol; It is 10～15% that oxidizing substance accounts for the mixed solution mass percent, and regeneration temperature is 80～120 ℃, and mass space velocity is 1～3h
-1, the recovery time is 4～8h;
4) molecular sieve catalyst after will regenerating feeds steam purging, and the steam purging temperature is 120～150 ℃, and mass space velocity is 1～3h
-1, purge time is 4～8h;
5) after steam purging finishes, switch nitrogen and purge, it is 120～170 ℃ that nitrogen purges temperature, and volume space velocity is 300～600h
-1, purge time is 3～5h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110045575 CN102151589B (en) | 2011-02-25 | 2011-02-25 | In-situ regeneration method for molecular sieve catalyst |
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| CN103182320B (en) * | 2011-12-29 | 2015-02-25 | 中国石油化工股份有限公司 | Regeneration method of titanium-silicon molecular sieve |
| CN103182321B (en) * | 2011-12-29 | 2014-12-31 | 中国石油化工股份有限公司 | Treatment method of deactivated titanium-silicon molecular sieve |
| CN103182319B (en) * | 2011-12-29 | 2014-12-31 | 中国石油化工股份有限公司 | Regeneration method of deactivated titanium-silicon molecular sieve |
| CN102872910B (en) * | 2012-09-29 | 2014-05-28 | 中国天辰工程有限公司 | Regeneration method of cyclohexene hydration catalyst |
| CN105080619A (en) * | 2014-05-14 | 2015-11-25 | 中国石油化工股份有限公司 | Protective agent for catalyst for olefin removal from aromatic hydrocarbon and its uses |
| CN104475175A (en) * | 2014-12-17 | 2015-04-01 | 烟台百川汇通科技有限公司 | Method for generating palladium catalyst for producing hydrogen peroxide by using anthraquinone process |
| CN105413758A (en) * | 2015-10-24 | 2016-03-23 | 中国海洋石油总公司 | Regeneration method for reformed aromatic hydrocarbon refining catalyst |
| CN105289757B (en) * | 2015-11-05 | 2018-10-02 | 中国海洋石油集团有限公司 | A kind of method of carbon remover in alkane dehydrogenating catalyst regenerative process |
| CN105363499A (en) * | 2015-12-02 | 2016-03-02 | 中国天辰工程有限公司 | In-situ regeneration method for Ti-Si molecular sieve catalyst |
| CN105879929A (en) * | 2016-04-21 | 2016-08-24 | 蚌埠学院 | Method for cleaning catalyst or/and carrier thereof |
| CN110152637A (en) * | 2018-02-25 | 2019-08-23 | 彭万喜 | The digester regeneration method of microenvironment pollution control |
| CN109433259B (en) * | 2018-10-31 | 2021-12-17 | 中海油天津化工研究设计院有限公司 | Method for in-situ modification of propylene epoxidation catalyst |
| CN112642476B (en) * | 2019-10-09 | 2023-04-07 | 中国石油化工股份有限公司 | Activity control method for in-situ coke removal of aromatic hydrocarbon olefin removal catalyst and application thereof |
| CN112691706A (en) * | 2020-12-23 | 2021-04-23 | 中触媒新材料股份有限公司 | Regeneration method of catalyst for preparing acetonitrile from ethanol |
| CN115178303B (en) * | 2021-04-02 | 2024-05-24 | 绍兴绿奕化工有限公司 | Method for recovering waste porous catalyst |
| CN113304773B (en) * | 2021-05-19 | 2022-09-20 | 万华化学集团股份有限公司 | In-situ regeneration method of deactivated titanium-silicon molecular sieve |
| CN116689043B (en) * | 2023-03-23 | 2025-06-10 | 华烁科技股份有限公司 | A method for removing coke from dimethyl oxalate hydrogenation catalyst |
| CN117000743A (en) * | 2023-08-17 | 2023-11-07 | 苏州禹江河智能科技有限公司 | A gas-phase catalytic cracking treatment process for low-concentration carbon crystalline organic waste |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070142215A1 (en) * | 2005-12-20 | 2007-06-21 | Chevron U.S.A. Inc. | Regeneration of ionic liquid catalyst by hydrogenation using a supported catalyst |
| CN101879432A (en) * | 2010-07-01 | 2010-11-10 | 中国石油化工股份有限公司 | Gas-solid contact equipment for fluidized bed |
| CN101935267A (en) * | 2010-07-14 | 2011-01-05 | 清华大学 | Acetylene hydrochlorination mercury-free catalyst fluidized bed continuous reaction regeneration device and process |
Family Cites Families (1)
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| JP2010188333A (en) * | 2009-02-18 | 2010-09-02 | Michio Uemura | Method of cleaning fluidized bed of diesel exhaust |
-
2011
- 2011-02-25 CN CN 201110045575 patent/CN102151589B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070142215A1 (en) * | 2005-12-20 | 2007-06-21 | Chevron U.S.A. Inc. | Regeneration of ionic liquid catalyst by hydrogenation using a supported catalyst |
| CN101879432A (en) * | 2010-07-01 | 2010-11-10 | 中国石油化工股份有限公司 | Gas-solid contact equipment for fluidized bed |
| CN101935267A (en) * | 2010-07-14 | 2011-01-05 | 清华大学 | Acetylene hydrochlorination mercury-free catalyst fluidized bed continuous reaction regeneration device and process |
Non-Patent Citations (1)
| Title |
|---|
| JP特开2010-188333A 2010.09.02 |
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