CN107382674B - Denitrification process of phenol products - Google Patents
Denitrification process of phenol products Download PDFInfo
- Publication number
- CN107382674B CN107382674B CN201710637158.3A CN201710637158A CN107382674B CN 107382674 B CN107382674 B CN 107382674B CN 201710637158 A CN201710637158 A CN 201710637158A CN 107382674 B CN107382674 B CN 107382674B
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- denitrification
- fixed bed
- catalyst
- pipeline
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
- C07C37/70—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment
- C07C37/82—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment by solid-liquid treatment; by chemisorption
-
- 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
- B01J29/90—Regeneration or reactivation
-
- 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
-
- 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
- B01J38/50—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using organic liquids
- B01J38/52—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using organic liquids oxygen-containing
-
- 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
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to the technical field of chemical industry, and particularly relates to a denitrification process for phenol products, in particular to a process for removing nitrides in phenol products such as phenol, m-cresol, p-cresol, o-cresol and the like. The method comprises the following specific steps: filling a catalyst into a fixed bed reactor, then injecting a phenol product to be denitrified, and carrying out continuous denitrification in the fixed bed; the catalyst is ZSM-5 molecular sieve or X-type molecular sieve or Y-type molecular sieve or beta molecular sieve or mordenite molecular sieve. The method has the advantages of high denitrification rate, easy separation, mild conditions, long service life, small environmental pollution, recycling and reuse, no reduction of denitrification effect after catalyst regeneration and the like.
Description
Technical Field
The invention belongs to the technical field of chemical industry, and particularly relates to a denitrification process for phenol products, in particular to a process for removing nitrides in phenol products such as phenol, m-cresol, p-cresol, o-cresol and the like.
Background
The nitride in the phenolic product mainly refers to organic nitride, and mainly comprises aniline, aliphatic amines, pyridine compounds and pyrrole compounds. The presence of organonitrogen compounds can affect the catalyst life and the stability of the phenolic product in subsequent reactions of the phenolic product. The current major denitrification techniques include hydrodenitrogenation and non-hydrodenitrogenation. The main methods for non-hydrodenitrogenation include: acid denitrification, solvent denitrification, complex process denitrification, combined process denitrification, adsorption denitrification, biological denitrification, microwave denitrification and the like. The hydrodenitrification can not solve the defects of low denitrification depth and the like, and the equipment investment and the operation cost are high; the problems of poor selectivity, environmental pollution, equipment corrosion and the like exist in acid denitrification; the solvent denitrification selectivity is poor; the separation is difficult to realize by the combined denitrification; the combined denitrification process is complex and has higher cost; the selection and culture of the strain by the biological denitrification method are difficult; microwave denitrification is currently in the laboratory stage. The adsorption denitrification method has the advantages of effectively removing the nitride in the fuel, mild conditions, easy separation, low investment, environmental friendliness and the like, and has the defects of low adsorption removal capacity, need of using a large amount of adsorbent when the nitrogen content in the oil product is high, and need of having good regeneration performance if the cost of the adsorbent is reduced.
Disclosure of Invention
In view of the above problems, the present invention is directed to: the denitrification process for efficiently removing the nitrides in the phenol products has the advantages of high denitrification rate, easiness in separation, mild condition, long service life, small environmental pollution, recycling and reusing, no reduction in denitrification effect after catalyst regeneration and the like.
The invention relates to a denitrification process of a phenol product, which comprises the following specific steps: filling a catalyst into a fixed bed reactor, then injecting a phenol product to be denitrified, and carrying out continuous denitrification in the fixed bed;
the catalyst is ZSM-5 molecular sieve or X-type molecular sieve or Y-type molecular sieve or beta molecular sieve or mordenite molecular sieve.
The molecular sieve SiO2/Al2O32.0-50.0, pore size of molecular sieve 0.1-2nm, and microporous surface area greater than or equal to 350m2/g。
The molecular sieve is an aluminosilicate with acid sites, and can achieve a good effect of removing basic nitrogen in the phenolic raw materials, thereby achieving the purpose of deep denitrification. Influence of the molecular sieve pore size on the denitrification effect: the molecular sieve has many cavities with same size, and the cavities have many micropores with same diameter, and these small holes have uniform diameter, and can adsorb the molecules with smaller diameter than the pore channel into the interior of the hole, and can reject the molecules with larger diameter than the pore channel, so that the molecules with different shapes and diameters, different polarity degrees, different boiling points and different saturation degrees can be separated. The aperture of the molecular sieve is too small, so that the alkaline nitride cannot enter the pore canal of the molecular sieve, and the adsorption of the alkaline nitride in the phenolic substances cannot be realized; the molecular sieve has too large aperture, phenols containing basic nitrides can easily pass through the pore channel, and the basic nitrides can not be adsorbed with higher efficiency, so that deep denitrification can not be realized. The influence of different silicon-aluminum ratios on the denitrification effect: different silicon-aluminum ratios result in molecular sieves with different numbers of acid sites, but the strength of the B acid is basically consistent, and the adsorption effect on nitrides is different because the probability of spatial proximity between acid centers is increased along with the increase of the acid centers, and the effect of multi-center adsorption of basic nitrides can occur, so that the adsorption is stronger. In the invention, the silicon-aluminum ratio of the molecular sieve is between 2 and 50, and the acting force between the molecular sieve and the alkaline nitride is strongest, thus achieving the effect of deep denitrification.
The catalyst filled in the fixed bed can be formed by extrusion molding or tabletting or granules.
The temperature of the denitrification process in the fixed bed is controlled between room temperature and 150 ℃, and the preferred temperature range is between 40 ℃ and 150 ℃. The temperature is too low, the molecular motion activity is low, and the adsorption effect of the molecular sieve on the nitride is poor; the temperature is too high, which causes high energy consumption, and the molecular motion activity is too high, which is easy to desorb from the surface of the catalyst, and affects the denitrification effect.
The sampling airspeed in the denitrification process is controlled to be 0.5h-1-5h-1. The airspeed is too small, and the raw material amount treated in unit time is small; the space velocity is too large, so that the raw material and the solid adsorbent cannot be in full contact, the residence contact time is shortened, and the denitrification rate is reduced.
The catalyst of the invention not only can deeply denitrify phenols, but also can realize in-situ regeneration, so the denitrification process of the phenol products also comprises the regeneration process of the catalyst.
Whether the catalyst is invalid or not is determined according to a chemiluminescence nitrogen determination instrument, the nitrogen content exceeds the production requirement, namely the catalyst is invalid, and the catalyst can be regenerated in an in-situ device in a fixed bed, so that the catalyst can be recycled.
The catalyst regeneration process comprises the following steps:
(1) purging the reaction solution: after stopping the feed, the mixture is passed through N2And blowing the pipeline of the fixed bed reactor to blow out the phenolic products in the pipeline. During purging of the reaction liquid, N2The blowing pressure is 0.3MPa-0.8 MPa. The pressure is too low to blow off phenols in the pipeline as much as possible; too much pressure tends to crush the shaped catalyst, resulting in pipe plugging.
(2) Ethanol cleaning: ethanol is pumped into the fixed bed reactor pipeline to clean the whole pipeline system. The amount of ethanol can be determined by those skilled in the art according to the size of the fixed bed and the pipeline, as long as clean cleaning is ensured. Soaking the fixed bed reactor with ethanol for 10-30 min, and performing N2And (5) purging.
(3)N2Purging: with N2Purging the entire fixed bed reactor pipeline, N2The blowing pressure is 0.3MPa-0.8 MPa.
(4) Activation and regeneration (air is added into the fixed bed system by an air pump in the whole activation process):
a. supplementing air into a gas phase pipeline of the fixed bed reactor through an air pump, and starting temperature programming at the same time;
b. the temperature is increased to 250-350 ℃ step by step;
c. heating for 0.5-5 h at the constant temperature of 250-350 ℃;
d. then the temperature is raised to 400-600 ℃ step by step;
e. heating for 0.5-5 h at the constant temperature of 400-600 ℃.
(5) And cooling the reactor. After the reactor is naturally cooled to 200-300 ℃, the hearth can be opened to accelerate cooling.
The reason why the catalyst adopts the temperature programming method is as follows: firstly, the collapse of catalyst pore channels caused by over-fast temperature rise is prevented; secondly, the temperature rise is too fast, which easily causes the unstable temperature control of the fixed bed and exceeds the set temperature.
In conclusion, the molecular sieve catalyst can remove the nitride in the phenol products by more than 98% under specific process conditions, has good denitrification effect, and has mild experimental conditions, and the phenol products are easy to separate from the molecular sieve; the catalyst can be regenerated in situ, the service life of the catalyst is prolonged, the cost is reduced, the environmental pollution is reduced, and the denitrification effect of the regenerated catalyst is not reduced.
Detailed Description
Example 1
The reaction temperature of the fixed bed reactor is 120 ℃, and the sampling airspeed is 0.5h-1Under the reaction conditions of (a): 100.0g of extruded strip-shaped beta molecular sieve catalyst, 11335.3g of m-cresol and p-cresol mixed raw material (containing 130ppm of nitrogen) is co-processed until the nitrogen content is less than 1.0ppm, the denitrification rate is 99 percent, and the denitrification amount of the catalyst reaches 14.62 mg/g.
The molecular sieve SiO2/Al2O325-30, the aperture of molecular sieve is 0.4-0.7nm, and the surface area of micropore is more than or equal to 350m2/g。
Example 2
The reaction temperature of the fixed bed reactor is 100 ℃, and the sampling airspeed is 5h-1Under the reaction conditions of (a): 150.0g extruded beta-moleculeSieving the catalyst, co-processing 20600.9g of m-cresol raw material (the nitrogen content is 110ppm) until the nitrogen content is less than 1.0ppm, the denitrification rate is 99 percent, and the denitrification amount of the catalyst reaches 14.97 mg/g.
The molecular sieve SiO2/Al2O325-30, the aperture of molecular sieve is 0.4-0.7nm, and the surface area of micropore is more than or equal to 350m2/g。
The catalyst regeneration comprises the following steps:
(1) purging the reaction solution: after stopping the feed, the mixture is passed through N2Purging the pipeline of the fixed bed reactor, and blowing out the phenol products in the pipeline; n is a radical of2The purge pressure of (2) was 0.3 MPa.
(2) Ethanol cleaning: pumping ethanol into a pipeline of the fixed bed reactor, and cleaning the whole pipeline system;
(3)N2purging: with N2Purging the whole fixed bed reactor pipeline; n is a radical of2The purge pressure of (2) was 0.8 MPa.
(4) Activation and regeneration:
a. supplementing air into a gas phase pipeline of the fixed bed reactor through an air pump, and starting temperature programming at the same time;
b. the temperature is increased to 250 ℃ step by step;
c. heating for 5h at the constant temperature of 250 ℃;
d. then, the temperature is increased to 400 ℃ step by step;
e. heating at 400 deg.C for 5 h.
(5) And cooling the reactor. After the reactor is naturally cooled to 200-300 ℃, the hearth is opened to accelerate the cooling.
Example 3
The catalyst regenerated in situ in example 2 was used, the reaction temperature was 150 ℃ and the space velocity of the sample injection was 2.5h-1Under the reaction conditions of (a): 150.0g of extruded strip-shaped beta molecular sieve catalyst is used for co-processing 20545.9g of p-cresol raw material (with the nitrogen content of 110ppm) until the nitrogen content is less than 1.0ppm, the denitrification rate is 99 percent, and the denitrification amount of the catalyst reaches 14.93 mg/g.
The catalyst regeneration comprises the following steps:
(1) purging the reaction solution: after stopping the feed, the mixture is passed through N2Blowing fixationA bed reactor pipeline for blowing off the phenol products in the pipeline; n is a radical of2The purge pressure of (2) was 0.8 MPa.
(2) Ethanol cleaning: pumping ethanol into a pipeline of the fixed bed reactor, and cleaning the whole pipeline system;
(3)N2purging: with N2Purging the whole fixed bed reactor pipeline; n is a radical of2The purge pressure of (2) was 0.3 MPa.
(4) Activation and regeneration:
a. supplementing air into a gas phase pipeline of the fixed bed reactor through an air pump, and starting temperature programming at the same time;
b. heating the mixture to 350 ℃ step by step;
c. heating at 350 deg.C for 0.5 h;
d. then, the temperature is increased to 600 ℃ step by step;
e. heating at 600 deg.C for 0.5 h.
(5) And cooling the reactor. After the reactor is naturally cooled to 200-300 ℃, the hearth is opened to accelerate the cooling.
Example 4
After the catalyst in example 3 is regenerated in situ in a fixed bed reactor, the reaction temperature is 100 ℃, and the sampling airspeed is 5h-1Under the reaction conditions of (a): 150.0g of strip-extruded beta molecular sieve catalyst, and co-processing 20587g of m-cresol and p-cresol mixed raw material (the nitrogen content is 110ppm) until the nitrogen content is less than 1.0ppm, wherein the denitrification rate is 99 percent, and the denitrification amount of the catalyst reaches 14.96 mg/g.
Example 5
The reaction temperature of the fixed bed reactor is 40 ℃, and the sampling airspeed is 0.5h-1Under the reaction conditions of (a): 120g of strip-extruded ZSM-5 molecular sieve catalyst, 13659.4g of phenol raw material (with nitrogen content of 130ppm) is co-processed until the nitrogen content is less than 2ppm, the denitrification rate is 98.3 percent, and the denitrification amount of the catalyst reaches 14.57 mg/g.
The molecular sieve SiO2/Al2O325.0-50.0, pore size of molecular sieve 0.5-0.7nm, and microporous surface area greater than or equal to 350m2/g。
Example 6
The reaction temperature in the fixed bed reactor is 60 DEGThe sample introduction airspeed is 0.5h-1Under the reaction conditions of (a): 120g of extruded strip-formed X-type molecular sieve catalyst, 16630.2g of o-cresol raw material (with the nitrogen content of 108ppm) is co-processed until the nitrogen content is less than 2ppm, the denitrification rate is 98.1 percent, and the denitrification amount of the catalyst reaches 14.69 mg/g.
The molecular sieve SiO2/Al2O32-3, the aperture of the molecular sieve is 0.1-0.3nm, and the surface area of the micropore is more than or equal to 350m2/g。
Example 7
The reaction temperature of the fixed bed reactor is 80 ℃, and the sampling airspeed is 0.5h-1Under the reaction conditions of (a): 120g of extruded strip-shaped Y-type molecular sieve catalyst is used for co-processing the meta-mixed phenol raw material (the nitrogen content is 98ppm)17989g until the nitrogen content is less than 2ppm, the denitrification rate is 98.7 percent, and the denitrification amount of the catalyst reaches 14.5 mg/g.
The molecular sieve SiO2/Al2O35-6, the aperture of the molecular sieve is 0.1-0.3nm, and the surface area of the micropore is more than or equal to 350m2/g。
Example 8
The reaction temperature of the fixed bed reactor is 80 ℃, and the sampling airspeed is 2.0h-1Under the reaction conditions of (a): 120g of the mordenite molecular sieve catalyst formed by extrusion molding is co-processed with 12744.6g of o-cresol raw material (the nitrogen content is 140ppm) until the nitrogen content is less than 2ppm, the denitrification rate is 99 percent, and the denitrification amount of the catalyst reaches 14.72 mg/g.
The molecular sieve SiO2/Al2O320-25, the aperture of the molecular sieve is 0.5-0.7nm, and the surface area of the micropore is more than or equal to 350m2/g。
The catalyst regeneration comprises the following steps:
(1) purging the reaction solution: after stopping the feed, the mixture is passed through N2Purging the pipeline of the fixed bed reactor, and blowing out the phenol products in the pipeline; n is a radical of2The purge pressure of (2) was 0.3 MPa.
(2) Ethanol cleaning: pumping ethanol into a pipeline of the fixed bed reactor, and cleaning the whole pipeline system;
(3)N2purging: with N2Purging the whole fixed bed reactor pipeline; n is a radical of2The purge pressure of (2) was 0.8 MPa.
(4) Activation and regeneration:
a. supplementing air into a gas phase pipeline of the fixed bed reactor through an air pump, and starting temperature programming at the same time;
b. the temperature is increased to 250 ℃ step by step;
c. heating for 5h at the constant temperature of 250 ℃;
d. then, the temperature is increased to 400 ℃ step by step;
e. heating at 400 deg.C for 5 h.
(5) And cooling the reactor. After the reactor is naturally cooled to 200-300 ℃, the hearth is opened to accelerate the cooling.
Example 9
After the catalyst in example 8 was regenerated in situ in a fixed bed reactor, the reaction temperature was 80 ℃ and the space velocity of the sample introduction was 2.0h-1Under the reaction conditions of (a): 120g of the mordenite molecular sieve catalyst formed by extrusion molding is co-processed with 12735.4g of o-cresol raw material (the nitrogen content is 140ppm) until the nitrogen content is less than 2ppm, the denitrification rate is 98.6 percent, and the denitrification amount of the catalyst reaches 14.65 mg/g.
Claims (3)
1. A denitrification process of phenolic products is characterized by comprising the following steps: the method comprises the following specific steps: filling a catalyst into a fixed bed reactor, then injecting a phenol product to be denitrified, and carrying out continuous denitrification in the fixed bed;
the catalyst is a ZSM-5 molecular sieve, an X-type molecular sieve, a Y-type molecular sieve, a beta molecular sieve or a mordenite molecular sieve;
the molecular sieve SiO2/Al2O3=2.0-50.0, the aperture of the molecular sieve is 0.1-2nm, and the surface area of the micropore is more than or equal to 350m2/g；
The denitrification temperature is 40-150 ℃;
the sampling airspeed of the phenol products is 0.5h-1-5 h-1。
2. The process of claim 1, wherein the denitrification process comprises: the denitrification process of the phenolic products also comprises a regeneration process of the catalyst, and the specific regeneration process comprises the following steps:
(1) purging the reaction solution: after stopping the feed, the mixture is passed through N2Purging the pipeline of the fixed bed reactor, and blowing out the phenol products in the pipeline;
(2) ethanol cleaning: pumping ethanol into a pipeline of the fixed bed reactor, and cleaning the whole pipeline system;
（3）N2purging: with N2Purging the whole fixed bed reactor pipeline;
(4) activation and regeneration:
a. supplementing air into a gas phase pipeline of the fixed bed reactor through an air pump, and starting temperature programming at the same time;
b. the temperature is increased to 250-350 ℃ step by step;
c. heating for 0.5-5 h at the constant temperature of 250-350 ℃;
d. then the temperature is raised to 400-600 ℃ step by step;
e. heating for 0.5-5 h at the constant temperature of 400-600 ℃;
(5) and cooling the reactor.
3. The process of claim 2, wherein the denitrification process comprises: n in steps (1) and (3)2The blowing pressure of the blowing device is 0.3MPa-0.8 MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710637158.3A CN107382674B (en) | 2017-07-31 | 2017-07-31 | Denitrification process of phenol products |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710637158.3A CN107382674B (en) | 2017-07-31 | 2017-07-31 | Denitrification process of phenol products |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107382674A CN107382674A (en) | 2017-11-24 |
| CN107382674B true CN107382674B (en) | 2020-12-01 |
Family
ID=60342346
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710637158.3A Active CN107382674B (en) | 2017-07-31 | 2017-07-31 | Denitrification process of phenol products |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107382674B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110627623B (en) * | 2019-09-06 | 2020-09-22 | 陕西煤业化工集团神木天元化工有限公司 | Separation system and method for alkaline nitride in phenol product |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3029294A (en) * | 1959-02-27 | 1962-04-10 | Hercules Powder Co Ltd | Purification of phenol |
| CN102816044A (en) * | 2012-08-30 | 2012-12-12 | 宁夏宝塔石化集团有限公司 | Method for basic nitrogen removal of benzene or methylbenzene serving as raw materials for alkylation reaction |
| CN102836743A (en) * | 2011-06-20 | 2012-12-26 | 中国石油化工股份有限公司 | Regeneration method of molecular sieve catalyst |
| CN103232326A (en) * | 2013-04-28 | 2013-08-07 | 南京工业大学 | Continuous production process for preparing phenol with benzene through hydroxylation |
| CN104557420A (en) * | 2013-10-11 | 2015-04-29 | 中国石油化工股份有限公司 | Toluene denitrification method |
-
2017
- 2017-07-31 CN CN201710637158.3A patent/CN107382674B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3029294A (en) * | 1959-02-27 | 1962-04-10 | Hercules Powder Co Ltd | Purification of phenol |
| CN102836743A (en) * | 2011-06-20 | 2012-12-26 | 中国石油化工股份有限公司 | Regeneration method of molecular sieve catalyst |
| CN102816044A (en) * | 2012-08-30 | 2012-12-12 | 宁夏宝塔石化集团有限公司 | Method for basic nitrogen removal of benzene or methylbenzene serving as raw materials for alkylation reaction |
| CN103232326A (en) * | 2013-04-28 | 2013-08-07 | 南京工业大学 | Continuous production process for preparing phenol with benzene through hydroxylation |
| CN104557420A (en) * | 2013-10-11 | 2015-04-29 | 中国石油化工股份有限公司 | Toluene denitrification method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107382674A (en) | 2017-11-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102070238B (en) | Process method for treating reverse osmosis concentrated water in refining waste water by ozone catalytic oxidization | |
| CN101560045A (en) | Coal chemical wastewater treating technique | |
| CN107376883B (en) | Regeneration method of activated carbon with saturated adsorption | |
| CN107382674B (en) | Denitrification process of phenol products | |
| RU2768802C2 (en) | Waste water treatment method | |
| CN108217811B (en) | System and method for simultaneously treating waste water containing organic matters and waste gas containing organic matters | |
| EP3463658B1 (en) | Process for preparing a catalyst and use thereof | |
| EP2984046B1 (en) | Process and installation for treating industrial water by means of physical separation, adsorption on resin et reverse osmosis | |
| CN104512943B (en) | Oxidized waste water reuse technology in a kind of aromatic carboxylic acid production process | |
| CN110642365A (en) | Method for advanced treatment of wastewater by subcritical oxidation technology | |
| BR112020009348A2 (en) | process to treat waste water from an industrial process to produce propylene oxide | |
| CN210528712U (en) | Processing system that high difficult degradation organic matter waste water discharged all up to standard | |
| CN102648038A (en) | Method and device for separating gaseous mixtures by means of permeation | |
| CN102718621B (en) | Method for selectively desorbing carbon disulfide in coarse benzene | |
| CN113562913A (en) | Treatment method of hydrazine hydrate production wastewater | |
| CN109205572B (en) | Method for purifying hydrogen peroxide | |
| EP3277626B1 (en) | Treating sulfuric acid | |
| CN109160491B (en) | Hydrogen peroxide purification method | |
| CN102464373A (en) | Method for removing benzopyrene from drinking water | |
| CN111225880A (en) | Method for removing boron and method for producing pure water or ultrapure water | |
| CN111115755B (en) | Treatment method of waste water in production of dye intermediate bromamine acid | |
| CN115430398B (en) | High-performance adsorbent and preparation method and application thereof | |
| RU2778318C2 (en) | Method for purification of wastewater | |
| CN115261064B (en) | Raw material pretreatment system and method for preparing alkyl aromatic hydrocarbon from Fischer-Tropsch light oil | |
| JPH1057949A (en) | Method of cleaning organic matter-containing water |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |