CN105665002B - A kind of regeneration method of inactive titanium silicon molecule sieve catalyst - Google Patents
A kind of regeneration method of inactive titanium silicon molecule sieve catalyst Download PDFInfo
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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
- 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
- B01J29/405—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 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/90—Regeneration or reactivation
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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
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
- B01J38/60—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using acids
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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
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
- B01J38/60—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using acids
- B01J38/62—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using acids organic
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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
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
- B01J38/64—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using alkaline material; using salts
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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
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
- B01J38/64—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using alkaline material; using salts
- B01J38/66—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using alkaline material; using salts using ammonia or derivatives thereof
Abstract
The present invention provides a kind of regeneration methods of inactive titanium silicon molecule sieve catalyst, include the following steps：Inactive titanium silicon molecule sieve catalyst mix with the acid solution containing cationic capturing agent, is washed till neutrality after stirring 1-10 hours at 20-120 DEG C, sour treated titanium-silicon molecular sieve catalyst is obtained after drying；Acid treated titanium-silicon molecular sieve catalyst is mixed with alkaline solution, the titanium-silicon molecular sieve catalyst in 150-190 DEG C of reaction 0.5-5 days at autogenous pressures, after obtaining alkali process；After the titanium-silicon molecular sieve catalyst filtering after alkali process, washing to pH value is 7-10, and regeneration titanium-silicon molecular sieve catalyst is obtained after drying and roasting.Regenerated titanium-silicon molecular sieve catalyst made from regeneration method of the present invention can effectively remove metal impurities and anatase, and activity and service life can reach fresh dose of level.
Description
Technical field
The invention belongs to the regeneration method fields of decaying catalyst, more particularly, to a kind of inactive titanium silicon molecule sieve catalyst
Regeneration method.
Background technique
TS-1 Titanium Sieve Molecular Sieve is that transition metal element titanium is introduced into one formed in the framework of molecular sieve with MFI structure
Kind has the novel titanosilicate of excellent selective paraffin oxidation catalytic performance.It not only has the catalysed oxidn of titanium, and has
Have the shape-selective effect and excellent stability of MFI, with excellent oxidisability and specific selectivity, can be widely applied to benzene,
In the oxidation reaction of the organic matters such as phenol, alcohols, ethers.Cyclohexanone oxamidinating and epoxidation of propylene etc. have been carried out industry at present
Metaplasia produces, furthermore the green catalysis system of TS-1 Titanium Sieve Molecular Sieve and hydrogen peroxide composition, avoids complex process and pollution environment
The problem of.
However, carrying out catalyst performance after a certain period of time in reaction can decline, the conversion ratio for being reflected as reaction is reduced, coloration
It increases, catalyst inactivation.EP 0496385 is reported, is needed in reaction process using periodically taking-up decaying catalyst and is supplemented fresh dose
Method maintain ideal catalytic activity.Also the conversion ratio of with good grounds reaction and selectivity be periodically or non-periodically in reagent production
Fresh dose is added to maintain catalytic activity, just needs to stop production to take out after catalyst accumulation is added to a certain amount of；Therefore, raising is urged
The stability and catalytic activity of agent are to actual production important in inhibiting.
It is generally believed that, there is following two reason in the reason of leading to catalyst inactivation：1, in Zeolite synthesis or reaction process
The metal impurities or byproduct of reaction of introducing assemble blocking catalyst internal gutter, so that molecular sieve activity bit quantity is reduced, lead
Cause catalytic activity decline；2, the skeleton of molecular sieve is present under the weakly alkaline environment of oximation reaction for a long time, and skeleton is gradually molten
Solution, destructurized, the titanium in simultaneous skeleton is lost.
CN03137913 discloses a kind of regeneration method, the catalyst of inactivation is handled in the acid solution of pH≤3, so
It is dry afterwards, roast after complete the regeneration of catalyst, but this method does not solve the skeleton dissolution of decaying catalyst and catalysis is caused to be lived
Property decline the problem of.
In the regeneration method of CN1302693A report, heat is carried out again after using dioxygen water process in the presence of inorganic fluoride
Processing is to complete catalyst regeneration process.But the method use fluorides, are also easy to produce virose fluoride in processes, have
Certain risk.
Summary of the invention
In view of this, the present invention is directed to propose a kind of regeneration method of inactive titanium silicon molecule sieve catalyst, utilizes the method
The metals content impurity and catalytic performance of treated decaying catalyst can be restored to fresh dose of level, and catalytic life can be restored to
The 60%~100% of fresh dose.
In order to achieve the above objectives, the technical proposal of the invention is realized in this way：
A kind of regeneration method of inactive titanium silicon molecule sieve catalyst, includes the following steps：
Step 1：Inactive titanium silicon molecule sieve catalyst is mixed with the acid solution containing cationic capturing agent, in 20-
It is washed till neutrality after stirring 1-10 hours at 120 DEG C, acid treated titanium-silicon molecular sieve catalyst is obtained after drying；
Step 2：Acid treated the titanium-silicon molecular sieve catalyst that step 1 obtains is mixed with alkaline solution, in 150-
190 DEG C are reacted 0.5-5 days at autogenous pressures, the titanium-silicon molecular sieve catalyst after obtaining alkali process；
Step 3：After titanium-silicon molecular sieve catalyst filtering after the alkali process that step 2 is obtained, washing to pH value is 7-
10, regeneration titanium-silicon molecular sieve catalyst is obtained after drying and roasting.
Further, the cationic capturing agent is ethylenediamine tetra-acetic acid, edetate, citric acid, citric acid
Salt, oxalic acid, oxalates, glutamic acid diacetic acid, glutamic acid diacetic acid salt, mixture one or more kinds of in ammonium chloride.
Further, the quality of the cationic capturing agent is the 1%-5% of inactive titanium silicon molecule sieve catalyst quality.
Further, the acid solution is to contain mixed solution one or more kinds of in sulfuric acid, nitric acid, hydrochloric acid.
Further, the mass concentration of the acid solution is 1%~15%.
Further, the acid solution and inactive titanium silicon molecule sieve catalyst mass ratio are (3-10)：1.
Further, the alkaline solution is to contain Tri-n-Propylamine, triethylamine, tetraethyl ammonium hydroxide, tetrapropyl hydrogen-oxygen
Change ammonium, tetrabutylammonium hydroxide, sodium hydroxide, mixed solution one or more kinds of in potassium hydroxide.
Further, the mass concentration of the alkaline solution is 1%~15%.
Further, the titanium-silicon molecular sieve catalyst mass ratio of the alkaline solution and inactivation is (3-10)：1.
Further, the inactive titanium silicon molecule sieve catalyst is in cyclohexanone oxamidinating reaction or epoxidation reaction of olefines
The titanium-silicon molecular sieve catalyst of middle inactivation, the titanium-silicon molecular sieve catalyst are TS-1 titanium-silicon molecular sieve catalyst.
Compared with the existing technology, the regeneration method of inactive titanium silicon molecule sieve catalyst of the present invention has following excellent
Gesture：
(1) regeneration method of the present invention is inactivated suitable for cyclohexanone oxamidinating reaction or epoxidation reaction of olefines
TS-1 titanium-silicon molecular sieve catalyst, ICP-MS (inductivity coupled plasma mass spectrometry) the result shows that, this method regeneration obtained
TS-1 titanium-silicon molecular sieve catalyst can effectively remove metal impurities；By life assessment, regenerated TS-1 titanium silicon molecule
The activity of sieve catalyst and service life can reach fresh dose of level.
(2) cationic capturing agent of the present invention can urging rapidly and efficiently under mildly acidic conditions with inactivation
Metal impurities contained in agent and the titanium in anatase form complex compound, can will be inactivated by better simply washing operation
Cation impurity in catalyst effectively removes, and total ion remaval rate can achieve 97% or more.
(3) the TS-1 titanium-silicon molecular sieve catalyst of inactivation of the present invention can achieve by the reprocessing of alkaline solution
The effect of secondary crystallization, used alkaline solution may be reused after the completion of use by heat treatment, energy conservation and environmental protection.
Specific embodiment
Unless otherwise stated, term used herein all has the meaning that those skilled in the art routinely understand, in order to
It is easy to understand the present invention, some terms used herein have been subjected to following definitions.
All number marks used in the specification and in the claims, such as pH, temperature, time, concentration, including
Range is all approximation.It is to be understood that although all plus term " about " before always not describing all number marks explicitly.
It will also be understood that, although not always specific narration, reagent described herein is only example, and equivalent is this field simultaneously
It is known.
Below with reference to embodiment, the present invention will be described in detail：
Catalyst is evaluated using continuous cyclohexanone Ammoximation reaction evaluating apparatus, reaction velocity is improved, using adding
Fast deactivation processes condition compares catalyst performance, and raw materials used is the industrial reagent of market purchase.The specific method is as follows：
Three-necked flask is placed in 77 ± 1 DEG C of water-baths, the 50ml tert-butyl alcohol, 8g cyclohexanone, 1g molecular sieve to be evaluated is added,
Alcohol ketone liquid and hydrogen peroxide are slowly added to micro-sampling pump respectively, and basic technological parameters are as follows：Hydrogen peroxide：The tert-butyl alcohol：Ammonia：Ring
Hexanone=1.05：1.5：3.3：1, material mean residence time 72 minutes, by obtained product 7890 chromatographic determination of Agilent
The conversion ratio of cyclohexanone and the selectivity of cyclohexanone oxime.
Wherein, yclohexanone conversion ratio=(amount of the remaining cyclohexanone of the amount-of the cyclohexanone of addition)/addition cyclohexanone
Amount × 100%；
Cyclohexanone oxime selectivity=the be converted to amount of the amount of cyclohexanone consumed by cyclohexanone oxime/conversion cyclohexanone ×
100%.The catalyst stabilization duration of runs is with yclohexanone conversion ratio>95% duration of runs meter.
Fresh dose is conventionally TS-1 titanium-silicon molecular sieve catalyst obtained, such as water described in following embodiment
Thermal synthesis method, same order elements synthetic method, the method that can also be recorded according to patent ZL201410082785.1 carry out TS-1 titanium silicon point
The synthesis of son sieve, and made after being modified according to the method that ZL201310022045.4 is recorded to the TS-1 Titanium Sieve Molecular Sieve of synthesis
?；The TS-1 titanium-silicon molecular sieve catalyst of the inactivation is fresh dose and transports in continuous cyclohexanone Ammoximation reaction evaluating apparatus
Inactivation sample after turning 60 hours.
Embodiment 1：
Hydrochloric acid solution, 0.3g grass by the TS-1 titanium-silicon molecular sieve catalyst of 30g inactivation and 300g mass concentration for 15%
Acid-mixed is closed, and is stirred 10 hours at 20 DEG C, dry after washing to neutrality；Add in TS-1 titanium-silicon molecular sieve catalyst after the drying
Enter the Tri-n-Propylamine solution that 90g mass concentration is 15%, be put into homogeneous reactor, taken out after being reacted 5 days under the conditions of 190 DEG C,
Centrifugation is washed, dry, is roasted 5 hours at 600 DEG C, and regeneration TS-1 titanium-silicon molecular sieve catalyst is obtained.
Embodiment 2：
Hydrochloric acid solution, 1.5g second two by the TS-1 titanium-silicon molecular sieve catalyst and 90g mass concentration of 30g inactivation for 1%
The mixing of amine tetraacethyl, is stirred 1 hour at 120 DEG C, dry after washing to neutrality；TS-1 titanium molecular sieve catalysis after the drying
The tetrapropylammonium hydroxide solution that 300g mass concentration is 1% is added in agent, is put into homogeneous reactor, it is anti-under the conditions of 150 DEG C
It takes out, is centrifuged after answering 3 days, wash, it is dry, it is roasted 5 hours at 600 DEG C, obtains regeneration TS-1 titanium-silicon molecular sieve catalyst.
Embodiment 3：
Nitric acid solution, 0.9g chlorination by the TS-1 titanium-silicon molecular sieve catalyst and 180g mass concentration of 30g inactivation for 3%
Ammonium mixing, is stirred 5 hours at 80 DEG C, dry after washing to neutrality；Add in TS-1 titanium-silicon molecular sieve catalyst after the drying
Enter the sodium hydroxide solution that 90g mass concentration is 1%, be put into homogeneous reactor, taken out after being reacted 0.5 day under the conditions of 150 DEG C,
Centrifugation is washed, dry, is roasted 5 hours at 600 DEG C, and regeneration TS-1 titanium-silicon molecular sieve catalyst is obtained.
Embodiment 4：
Hydrochloric acid solution, 0.3g by the TS-1 titanium-silicon molecular sieve catalyst and 240g mass concentration of 30g inactivation for 5%
The mixing of 0.3g ammonium chloride, is stirred 3 hours at 100 DEG C, dry after washing to neutrality；TS-1 Titanium Sieve Molecular Sieve after the drying is urged
The tetrabutylammonium hydroxide solution that 150g mass concentration is 8% is added in agent, homogeneous reactor is put into, under the conditions of 160 DEG C
Reaction is taken out after 3 days, is centrifuged, and is washed, dry, is roasted 5 hours at 600 DEG C, and regeneration TS-1 titanium-silicon molecular sieve catalyst is obtained.
Embodiment 5：
Sulfuric acid solution, 0.9g lemon by the TS-1 titanium-silicon molecular sieve catalyst and 240g mass concentration of 30g inactivation for 5%
Acid-mixed is closed, and is stirred 8 hours at 60 DEG C, dry after washing to neutrality；Add in TS-1 titanium-silicon molecular sieve catalyst after the drying
Enter the tetraethyl ammonium hydroxide solution that 90g mass concentration is 3%, homogeneous reactor is put into, after reacting 1 day under the conditions of 150 DEG C
It takes out, is centrifuged, wash, it is dry, it is roasted 5 hours at 600 DEG C, obtains regeneration TS-1 titanium-silicon molecular sieve catalyst.
Embodiment 6：
Hydrochloric acid solution, 2.0g paddy ammonia by the TS-1 titanium-silicon molecular sieve catalyst and 150g mass concentration of 30g inactivation for 7%
Sour sodium diacelate mixing, is stirred 5 hours at 80 DEG C, dry after washing to neutrality；TS-1 Titanium Sieve Molecular Sieve after the drying is urged
The Tri-n-Propylamine solution that 150g mass concentration is 7% is added in agent, is put into homogeneous reactor, is reacted 2 days under the conditions of 180 DEG C
After take out, be centrifuged, wash, it is dry, roast 5 hours at 600 DEG C, obtains regenerating TS-1 titanium-silicon molecular sieve catalyst.
Embodiment 7：
Sulfuric acid solution, 0.6g second two by the TS-1 titanium-silicon molecular sieve catalyst and 90g mass concentration of 30g inactivation for 10%
The mixing of amine tetraacethyl, is stirred 6 hours at 60 DEG C, dry after washing to neutrality；TS-1 titanium molecular sieve catalysis after the drying
The Tri-n-Propylamine solution that 90g mass concentration is 10% is added in agent, homogeneous reactor is put into, after reacting 4 days under the conditions of 170 DEG C
It takes out, is centrifuged, wash, it is dry, it is roasted 5 hours at 600 DEG C, obtains regeneration TS-1 titanium-silicon molecular sieve catalyst.
The ICP-MS knot of regeneration TS-1 titanium-silicon molecular sieve catalyst made from embodiment 1-7, fresh dose and deactivator
Fruit is shown in Table 1, and life assessment is shown in Table 2, it can be seen from Table 1 that the regeneration catalyzing obtained using regeneration method of the present invention
Agent；It can be seen from Table 2 that the activity of regenerated catalyst and service life can reach fresh dose of level.
1 catalyst ICP-MS result of table
The evaluation of 2 catalyst life of table
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Within mind and principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (8)
1. a kind of regeneration method of inactive titanium silicon molecule sieve catalyst, it is characterised in that：The regeneration method includes the following steps：
Step 1：Inactive titanium silicon molecule sieve catalyst is mixed with the acid solution containing cationic capturing agent, in 20-120 DEG C
Lower stirring is washed till neutrality after 1-10 hours, acid treated titanium-silicon molecular sieve catalyst is obtained after drying；
Step 2：Acid treated the titanium-silicon molecular sieve catalyst that step 1 obtains is mixed with alkaline solution, in 150-190 DEG C
It reacts 0.5-5 days at autogenous pressures, the titanium-silicon molecular sieve catalyst after obtaining alkali process；
Step 3：After titanium-silicon molecular sieve catalyst filtering after the alkali process that step 2 is obtained, washing to pH value is 7-10, then
Regeneration titanium-silicon molecular sieve catalyst is obtained after drying and roasting；
Wherein, the cationic capturing agent be ethylenediamine tetra-acetic acid, edetate, citric acid, citrate, oxalic acid,
Oxalates, glutamic acid diacetic acid, glutamic acid diacetic acid salt, mixture one or more kinds of in ammonium chloride；
The alkaline solution is to contain Tri-n-Propylamine, triethylamine, tetraethyl ammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydrogen
Amine-oxides, sodium hydroxide, a kind of solution or two or more mixed solutions in potassium hydroxide.
2. the regeneration method of inactive titanium silicon molecule sieve catalyst according to claim 1, it is characterised in that：The cation
The quality of capturing agent is the 1%-5% of inactive titanium silicon molecule sieve catalyst quality.
3. the regeneration method of inactive titanium silicon molecule sieve catalyst according to claim 1, it is characterised in that：The acidity is molten
Liquid is to contain solution a kind of in sulfuric acid, nitric acid, hydrochloric acid or two or more mixed solutions.
4. the regeneration method of inactive titanium silicon molecule sieve catalyst as claimed in claim 3, it is characterised in that：The acid solution
Mass concentration is 1%~15%.
5. the regeneration method of inactive titanium silicon molecule sieve catalyst according to claim 1, it is characterised in that：The acidity is molten
Liquid and inactive titanium silicon molecule sieve catalyst mass ratio are (3-10)：1.
6. the regeneration method of inactive titanium silicon molecule sieve catalyst described in claim 5, it is characterised in that：The alkaline solution
Mass concentration is 1%~15%.
7. the regeneration method of inactive titanium silicon molecule sieve catalyst according to claim 6, it is characterised in that：The alkalinity is molten
Liquid and inactive titanium silicon molecule sieve catalyst mass ratio are (3-10)：1.
8. the regeneration method of -7 any inactive titanium silicon molecule sieve catalysts according to claim 1, it is characterised in that：It is described
Inactive titanium silicon molecule sieve catalyst is that the Titanium Sieve Molecular Sieve inactivated in cyclohexanone oxamidinating reaction or epoxidation reaction of olefines is urged
Agent, the titanium-silicon molecular sieve catalyst are TS-1 titanium-silicon molecular sieve catalyst.
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| CN106082259A (en) * | 2016-06-17 | 2016-11-09 | 齐鲁工业大学 | There is overlength catalytic life HTS and low cost preparation method thereof |
| CN108126744A (en) * | 2017-12-29 | 2018-06-08 | 镇江巨茂分子筛有限公司 | The regeneration technology of preparing ethylbenzene from dry gas catalyst |
| CN110075914A (en) * | 2019-05-28 | 2019-08-02 | 江苏扬农化工集团有限公司 | A kind of method of HPPO technique inactive titanium silicon molecule sieve catalyst in-situ regeneration |
| CN110152726A (en) * | 2019-05-28 | 2019-08-23 | 江苏扬农化工集团有限公司 | The regeneration method of inactive titanium silicon molecule sieve catalyst in a kind of HPPO technique |
| CN110256376B (en) * | 2019-06-14 | 2022-07-19 | 大连理工大学 | Fluidized reaction method for synthesizing propylene oxide by hydrogen peroxide gas phase epoxidation |
| CN114453019B (en) * | 2020-11-09 | 2023-07-11 | 中国石油化工股份有限公司 | Reactivation method of ethylbenzene catalyst |
| CN112675907B (en) * | 2021-01-08 | 2021-11-09 | 中国科学院大连化学物理研究所 | In-situ combined regeneration method of deactivated titanium-silicon molecular sieve catalyst |
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| CN102824926A (en) * | 2012-09-03 | 2012-12-19 | 中国天辰工程有限公司 | Regeneration method of inactivated titanium silicon molecular sieve |
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| CN101602011A (en) * | 2009-07-08 | 2009-12-16 | 华东师范大学 | A kind of renovation process of titanium-silicon molecular sieve catalyst |
| CN103182322A (en) * | 2011-12-29 | 2013-07-03 | 中国石油化工股份有限公司 | Treatment method of inactivated titanium silicon molecular sieve |
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