CN109277115A - The preparation method of catalyst for etherification and the method for producing o-methoxy toluene - Google Patents
The preparation method of catalyst for etherification and the method for producing o-methoxy toluene Download PDFInfo
- Publication number
- CN109277115A CN109277115A CN201710595153.9A CN201710595153A CN109277115A CN 109277115 A CN109277115 A CN 109277115A CN 201710595153 A CN201710595153 A CN 201710595153A CN 109277115 A CN109277115 A CN 109277115A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- etherification
- preparation
- molecular sieve
- hours
- 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.)
- Pending
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J29/42—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 iron group metals, noble metals or copper
- B01J29/46—Iron group metals or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7007—Zeolite Beta
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7042—TON-type, e.g. Theta-1, ISI-1, KZ-2, NU-10 or ZSM-22
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/76—Iron group metals or copper
- B01J29/7615—Zeolite Beta
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/76—Iron group metals or copper
- B01J29/7684—TON-type, e.g. Theta-1, ISI-1, KZ-2, NU-10 or ZSM-22
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/09—Preparation of ethers by dehydration of compounds containing hydroxy groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention provides a kind of preparation method of catalyst for etherification, which comprises a) roasts 4 to 10 hours by molecular sieve and binder mixed-forming and at 500 to 700 DEG C；C) oxide modifying is carried out to product obtained in previous step and is roasted 3 to 10 hours at 550 to 700 DEG C, wherein the oxide is selected from one of alkaline earth oxide and transition metal oxide or a variety of；And d) to product obtained in previous step 300 to 800 DEG C progress steam treatment 0.5 to 10 hour, wherein step c) and step d) implementation sequence can be interchanged.The present invention also provides a kind of methods for producing o-methoxy toluene by etherification reaction as raw material using o-cresol and methanol using above-mentioned catalyst for etherification.Catalyst according to the invention stability is good, corrodes in production process without equipment, is a kind of environmental-friendly catalyst, has good prospects for commercial application.
Description
Technical field
The present invention relates to catalytic fields, and in particular, to a kind of preparation method of catalyst for etherification and with o-cresol and
Methanol is the method that raw material produces o-methoxy toluene by etherification reaction.
Background technique
O-methoxy toluene also known as 2- methylanisole, are colourless liquids, are used for organic synthesis, also serve as solvent, fragrance
And pest repellant, and new herbicides processed are used in pesticide industry.The preparation process of traditional o-methoxy toluene is adjacent methyl
Phenol is made with dimethyl suflfate through methylation reaction in the presence of sodium hydroxide.It is washed after reaction through neutralizing, multi_layer extraction；Subtract
Pressure distills and obtains finished product.The technique uses the dimethyl suflfate of severe toxicity as raw material, seriously polluted.
Contain a large amount of o-cresol in coal tar, since cresols market demand is few, traditional technology is coal tar
Using adding hydrogen to prepare aromatic hydrocarbons, hydrogen consumption is big in the technical process, less economical.By adjacent from o-cresol and methanol etherification reaction production
Methylanisole, o-methoxy toluene can be used as gasoline high-knock rating gasoline component additive, have a vast market foreground.
Therefore, it develops a kind of new for producing o-methoxy toluene by etherification reaction using o-cresol and methanol as raw material
Catalyst and using its produce o-methoxy toluene method have great importance.
Summary of the invention
From technical problem described above, the purpose of the present invention is to provide one kind using o-cresol and methanol as raw material
The method of shape-selective etherificate production o-methoxy toluene.According to the technique and scheme of the present invention, using o-cresol and methanol as raw material, to change
Property molecular sieve be catalyst, for the selectivity of o-methoxy toluene up to 95%, catalyst stability is good.Without equipment in production process
Corrosion is a kind of environmental-friendly technique, has good prospects for commercial application.
The present inventor passes through thoroughgoing and painstaking research, completes the present invention.
According to an aspect of the invention, there is provided a kind of preparation method of catalyst for etherification, which comprises
A) it is roasted 4 to 10 hours by molecular sieve and binder mixed-forming and at 500 to 700 DEG C；
C) oxide modifying is carried out to product obtained in previous step and is roasted 3 to 10 hours at 550 to 700 DEG C,
Wherein the oxide is selected from one of alkaline earth oxide and transition metal oxide or a variety of；With
D) to product obtained in previous step 300 to 800 DEG C progress steam treatment 0.5 to 10 hour,
Wherein the implementation sequence of step c) and step d) can be interchanged.
Certain preferred embodiments according to the present invention, the method also includes the following steps b) of follows step a):
B) sour processing is carried out to product obtained in step a) and is roasted 2 to 10 hours at 500 to 600 DEG C.
Certain preferred embodiments according to the present invention, the molecular sieve be selected from ZSM-5 molecular sieve, MCM-22 molecular sieve and
One of BETA molecular sieve is a variety of.
Certain preferred embodiments according to the present invention, the silica alumina ratio of the molecular sieve are 20: 1 to 80: 1.
Certain preferred embodiments according to the present invention, the molecular sieve are hydrogen type molecular sieve or ammonium type molecular sieve.
Certain preferred embodiments according to the present invention, the binder is in silica solution, diatomite and silica
It is one or more of.
Certain preferred embodiments according to the present invention, based on the total weight of the silica solution, the silica solution includes weight
Measure the silica that percentage is 20%-40%.
Certain preferred embodiments according to the present invention, in step a), the weight of the molecular sieve and the binder
Than being 30: 70 to 85: 15.
Certain preferred embodiments according to the present invention, the alkaline-earth metal are selected from one of calcium, magnesium and barium or a variety of,
And the alkaline earth oxide is selected from one of calcium oxide, magnesia and barium monoxide or a variety of；The transition metal choosing
From one of iron and nickel or a variety of, and the transition metal oxide is selected from one of iron oxide and nickel oxide or more
Kind.
Certain preferred embodiments according to the present invention, the oxide modifying include: the product for obtaining previous step
It is impregnated in the acid salt of the alkaline-earth metal or the acid salt of the transition metal and then to impregnate in products therefrom
The alkaline-earth metal acid salt or the transition metal acid salt thermal decomposition, with generate the alkaline earth oxide or
The transition metal oxide.
Certain preferred embodiments according to the present invention are based on step c) when carrying out the modification of alkaline earth oxide
Obtained in product total weight, the content of the alkaline earth oxide in product obtained in step c) is 0.1 to 10 weight
Measure %.
Certain preferred embodiments according to the present invention are based on step c) when carrying out the modification of transition metal oxide
Obtained in product total weight, the content of the transition metal oxide in product obtained in step c) is 0.1 to 10 weight
Measure %.
Certain preferred embodiments according to the present invention, the steam treatment are saturated steam processing.
Certain preferred embodiments according to the present invention, the acid processing includes by product obtained in step a) inorganic
Normal temperature dipping 4 to 24 hours in acid, or product obtained in step a) is small in 30 to 80 DEG C of dippings 4 to 12 in organic acid
When.
Certain preferred embodiments according to the present invention, the inorganic acid are selected from one of nitric acid and sulfuric acid or a variety of,
And the organic acid is selected from one of citric acid and oxalic acid or a variety of.
According to another aspect of the present invention, it provides one kind and passes through etherification reaction production using o-cresol and methanol as raw material
The method of o-methoxy toluene, which comprises in 250 to 500 DEG C of reaction temperatures, 0.5 to 20h-1Feed weight it is empty
Under speed and condition of normal pressure, o-cresol, methanol and carrier gas are mixed to and are had by load the catalyst bed of catalyst for etherification
Layer, the catalyst for etherification is prepared by preparation method as described above.
Certain preferred embodiments according to the present invention, the carrier gas are nitrogen or vapor.
The molar ratio of certain preferred embodiments according to the present invention, o-cresol and methanol is 1: 10 to 1: 3, and described
The molar ratio of carrier gas and o-cresol is 0.5: 1 to 20: 1.
The beneficial effect of the present invention compared with the existing technology is:
(1) a kind of method by o-cresol methanol etherification production o-methoxy toluene is provided, catalyst performance is excellent, surely
It is qualitative good.Catalyst preparation process is simple, and preparation cost is low.With traditional o-cresol be etherified production process compared with, production process without
Pollution is a kind of environmentally protective novel technique.
(2) have the advantages that production procedure is simple using this method production o-methoxy toluene, with traditional production technology
It compares, production cost can be greatly lowered, it is with good economic efficiency.
Specific embodiment
Below with reference to specific embodiment, present invention is further described in detail.It will be appreciated that, it is contemplated that other realities
Mode is applied, and does not depart from the scope or spirit of the invention, it is possible to implement these other embodiments.Therefore, below to retouch in detail
It states and is non-limiting.
Unless otherwise specified, expression characteristic size, quantity and materialization used in specification and claims are special
All numbers of property be construed as to be modified by term " about " in all cases.Therefore, unless there are opposite
Illustrate, the numerical parameter otherwise listed in description above and the appended claims is approximation, those skilled in the art
Member can seek the required characteristic obtained using teachings disclosed herein, suitably change these approximations.With endpoint table
The use for the numberical range shown includes all numbers within the scope of this and any range within the scope of this, for example, 1 to 5 includes
1,1.1,1.3,1.5,2,2.75,3,3.80,4 and 5 etc..
The technical issues of present invention foundation is solved is that traditional methyl phenyl ethers anisole adds in hydrogen aromatic hydrocarbons technology, and hydrogen consumption is high, economy
The disadvantage of difference, the present invention provide a kind of using o-cresol and methanol as the method for the shape-selective etherificate production o-methoxy toluene of raw material.Root
According to technical solution of the present invention, using o-cresol and methanol as raw material, gas phase is etherified highly selective life over a molecular sieve catalyst
O-methoxy toluene is produced, production process does not corrode equipment, do not generate a large amount of industrial wastewater, is a kind of environmental-friendly green work
Skill.
Specifically, the present invention provides a kind of preparation method of catalyst for etherification, which comprises
A) it is roasted 4 to 10 hours by molecular sieve and binder mixed-forming and at 500 to 700 DEG C；
C) oxide modifying is carried out to product obtained in previous step and is roasted 3 to 10 hours at 550 to 700 DEG C,
Wherein the oxide is selected from one of alkaline earth oxide and transition metal oxide or a variety of；With
D) to product obtained in previous step 300 to 800 DEG C progress steam treatment 0.5 to 10 hour,
Wherein the implementation sequence of step c) and step d) can be interchanged.
Preferably, the method also includes the following steps b) of follows step a):
B) sour processing is carried out to product obtained in step a) and is roasted 2 to 10 hours at 500 to 600 DEG C.
Selected molecular sieve is selected from ZSM-5 molecular sieve, MCM-22 molecular sieve and BETA according to the technique and scheme of the present invention
One of molecular sieve molecular sieve is a variety of.MCM-49 molecular sieve of the present invention is according in patent US5236575
Method synthesis；MCM-22 molecular sieve is synthesized according to the method in patent US4954325；ZSM-5 molecular sieve is big by Nankai
The production of chemical catalyst factory, name of product NKF-5；BETA molecular sieve is produced by Catalyst Factory, Nankai Univ, name of product
For NKF-6.
In order to which technical effect of the invention is better achieved, the silica alumina ratio of the molecular sieve is 20: 1 to 80: 1, excellent
Select 30: 1 to 60: 1, more preferable 30: 1 to 40: 1.
Preferably, the molecular sieve is hydrogen type molecular sieve or ammonium type molecular sieve.Disclosure according to the present invention, the hydrogen
Type molecular sieve or ammonium type molecular sieve are anti-to molecular sieve progress hydrogenation or ammoniumization by preparation method conventional in the art
It should prepare.
In order to enable catalyst for etherification can bond and convenient for subsequent molding, in catalyst for etherification according to the present invention
Preparation method in use binder.The binder is neutral oxide.The binder be selected from silica solution, diatomite and
One or more of silica.It is preferably based on the total weight of the silica solution, the silica solution is comprising weight percent
The silica of 20%-40%.Wherein in step a), the weight ratio of the molecular sieve and the binder is 30: 80 to 85:
15, preferably 40: 60 to 80: 20, and more preferable 65: 35 to 70: 30.
According to the technique and scheme of the present invention, oxide modifying is carried out simultaneously to product obtained in previous step in step c)
And roasted 3 to 10 hours at 550 to 700 DEG C, wherein the oxide is selected from alkaline earth oxide and transition metal oxide
One of or it is a variety of.The alkaline-earth metal is selected from one of calcium, magnesium and barium or a variety of, and the alkaline earth oxide
Selected from one of calcium oxide, magnesia and barium monoxide or a variety of；The transition metal is selected from one of iron and nickel or a variety of,
And the transition metal oxide is selected from one of iron oxide and nickel oxide or a variety of.Preferably, the oxide modifying
Include: product obtained in upper one is impregnated in the acid salt of the alkaline-earth metal or the acid salt of the transition metal and
Make the acid salt thermal decomposition of the acid salt or the transition metal of the alkaline-earth metal impregnated in products therefrom, then to produce
The raw alkaline earth oxide or the transition metal oxide.Wherein, when carrying out the modification of alkaline earth oxide, base
The content of the total weight of the product obtained in step c), the alkaline earth oxide in product obtained in step c) is 0.1
To 10 weight %, preferably 1 to 8 weight %, and more preferable 3 to 5 weight %.In addition, when carrying out changing for transition metal oxide
Property when, based on the total weight of product obtained in step c), transition metal oxide in product obtained in step c) contains
Amount is 0.1 to 10 weight %, preferably 1 to 8 weight %, and more preferable 3 to 5 weight %.
According to the technique and scheme of the present invention, product obtained in previous step is carried out at 300 to 800 DEG C in step d)
Steam treatment 0.5 to 10 hour.The steam treatment is saturated steam processing.
According to the technique and scheme of the present invention, in step b) to product obtained in step a) carry out sour processing and
500 to 600 DEG C roast 2 to 10 hours.The acid processing includes by normal temperature dipping 4 in mineral acid of product obtained in step a)
It is impregnated 4 to 12 hours in organic acid at 30 to 80 DEG C to 24 hours, or by product obtained in step b).
To acid processing in use acid type be not particularly limited, it is preferable that the inorganic acid be selected from nitric acid and
One of sulfuric acid is a variety of, and the organic acid is selected from one of citric acid and oxalic acid or a variety of.
At this it should be further noted that due to appearance in the characteristics of preparation process considers molecular sieve structure and molecular sieve
The quantity of face acidic site is optimized and is controlled to percentage shared by modifying agent in modified step and catalyst, when molding
Using silica, silica solution and diatomite, increase the silicone hydroxyl of molecular sieve surface after roasting.Carry out sour processing, steam treatment
Enhance the hydrothermal stability of catalyst, the synergistic effect of exactly these types of modifying process, so that catalyst has good catalytic
Can, the intensity of catalyst is good, is able to satisfy industrial application requirement completely.
Catalyst preparation process is molecular sieve, adhesive mixed-forming, molding mode can be spray drying or extrusion at
Type.Molecular sieve can be the ZSM-5 and MCM-22 of Hydrogen or ammonia type, BETA molecular sieve.Molecular sieve after molding carries out sour processing,
Can be nitric acid, sulfuric acid, 30 DEG C dipping 4-24 hours, using organic acid citric acid, oxalic acid, 80 DEG C dipping 4-12 hours.According to
Outer surface acidity is different, needs to carry out different metal oxide modifieds.350 DEG C -800 DEG C of steam treatment temperature are advisable,
100% steam treatment 0.5-10 hours.
According to molding mode difference, fluid catalyst or fixed bed catalyst can be used as.By above-mentioned after spray shaping
Preparation step, can be prepared by fluid catalyst.Extruded moulding can be prepared by fixed bed catalyst through above-mentioned steps for parent.
It should be noted that the various method of modifying of catalyst, are the acid strength and different acidity sieved according to parent molecule
The density of position is different and different, and various method of modifying are composite modified used in the present invention obtains required catalyst.For urging
The lesser molecular sieve parent of the acid site density of agent, just can be obtained preferably using one or two kinds of method of modifying of the invention
Acid site density.Therefore, the single method of modifying of various elements also belongs to and of the invention covers field.For example, metal oxide
Modified, the single modification such as steam treatment all belongs to the scope of the present invention.
The present invention also provides a kind of sides for producing o-methoxy toluene by etherification reaction using o-cresol and methanol as raw material
Method, which comprises in 250 to 500 DEG C of reaction temperatures, 0.5 to 20h-1Feed weight air speed and condition of normal pressure under,
O-cresol, methanol and carrier gas are mixed to and are had by load the catalyst bed of catalyst for etherification, the catalyst for etherification
It is to be prepared by preparation method as described above.
The carrier gas is for dispersing and diluting o-cresol and methanol.Preferably, carrier gas is nitrogen or vapor.
According to the present invention from the method that o-cresol and methanol produce o-methoxy toluene by etherification reaction, adjacent first
The molar ratio of phenol and methanol is 1: 10 to 1: 3, preferably 1: 8 to 1: 4, more preferable 1: 6 to 1: 5；And the carrier gas and adjacent first
The molar ratio of phenol is 0.5: 1 to 20: 1, preferably 1: 1 to 10: 1, more preferable 3: 1 to 5: 1.
The present invention is described in more detail below with reference to embodiment.It may be noted that these descriptions and embodiment are all
In order to be easy to understand the present invention, rather than limitation of the present invention.Protection scope of the present invention is with appended claims
It is quasi-.
Embodiment
In the present invention, unless otherwise noted, used reagent is commercial products, is directly used without further
Purification process.In addition, mentioned " % " is " weight % ", and mentioned " part " is " parts by weight ".
Embodiment 1
The preparation process of catalyst is as follows: by mole silica alumina ratio be 20 120 grams of HZSM-5 molecular sieve and 60 grams of diatomite,
100 grams of silica solution comprising weight percent for 20% silica mix, and it is crowded as helping that suitable 10% dust technology is added
Agent extruded moulding.120 DEG C of drying, 500 DEG C roast 10 hours.Above-mentioned catalyst is cut into 1-3mm, cylindrical catalyst parent is made
A0.20 grams of precursor catalyst A0 is added to the aqueous solution of nitric acid of 50ml weight content 10%, 30 DEG C are impregnated 4 hours.120 DEG C of bakings
It is dry, 550 DEG C of roastings, 10 hours obtained A1.20 grams of A1 are carried out steam treatment 10 hours in 100% steam atmosphere, are handled
Temperature is 550 DEG C, and 20 grams of A2 sample is used concentration for the calcium nitrate water of 0.18 weight % by 550 DEG C of roastings, 3 hours obtained A2
Solution impregnates 24 hours, 120 DEG C of drying, and 600 DEG C roast 3 hours, and it is 0.1% that weight percent calcium is aoxidized in catalyst, is made
Catalyst A, wherein molecular sieve content is 60%.
Embodiment 2
The preparation process of catalyst is as follows: mole silica alumina ratio is included weight for 30 170 grams of HZSM-5 molecular sieve and 100g
The silica solution mixing for measuring the silica that percentage is 30%, is added suitable 10% dust technology as extrusion aid extruded moulding.
120 DEG C of drying, 700 DEG C roast 4 hours.Above-mentioned catalyst is cut into 1-3mm, cylindrical catalyst parent B0 is made.By 20 grams of mother
The aqueous solution of nitric acid of 50ml weight content 10% is added in body catalyst B0, and 30 DEG C are impregnated 10 hours.120 DEG C of drying, then 800 DEG C
Roast 2 hours obtained B1.Concentration is used to impregnate 12 hours, 120 DEG C for the barium nitrate aqueous solution of 1 weight % in 20 grams of B1 sample
Drying, 550 DEG C roast 10 hours, and barium monoxide weight content is 1%, and B2 is made.By 20 grams of B2 in 100% steam atmosphere into
Row steam treatment 0.5 hour, treatment temperature was 800 DEG C, 550 DEG C of roastings, 3 hours obtained catalyst B.Molecular sieve in catalyst
Content is 85%.
Embodiment 3
The preparation process of catalyst is as follows: by mole silica alumina ratio be 40 200 grams of HZSM-5 molecular sieve and 20 grams of diatomite,
100 grams of silica solution comprising weight percent for 30% silica mix, and it is crowded as helping that suitable 10% dust technology is added
Agent extruded moulding.120 DEG C of drying, 550 DEG C roast 4 hours.Above-mentioned catalyst is cut into 1-3mm, cylindrical catalyst parent is made
D0.20 grams of precursor catalyst D0 is added to the aqueous sulfuric acid of 50ml weight content 1%, 30 DEG C are impregnated 24 hours.120 DEG C of bakings
It is dry, 600 DEG C of roastings, 3 hours obtained D1.Concentration is used to impregnate 24 for the calcium nitrate aqueous solution of 1.8 weight % in 20 grams of D1 sample
Hour, 120 DEG C of drying, 600 DEG C roast 3 hours, and it is 1% that weight percent calcium is aoxidized in catalyst, and D2 is made.20 grams of D2 are existed
It is carried out steam treatment 10 hours in 100% steam atmosphere, treatment temperature is 350 DEG C, and 550 DEG C are made catalysis in roasting 3 hours
Agent D.The content that molecular sieve in catalyst is made is 80%.
Embodiment 4
The preparation process of catalyst is as follows: being 30 200 grams of ammonia type ZSM-5 molecular sieve and 10 grams of diatoms by mole silica alumina ratio
Native, 100 grams of silica solution comprising the silica that weight percent is 40% mix, and suitable 10% dust technology of addition, which is used as, to be helped
Squeeze agent extruded moulding.120 DEG C of drying, 550 DEG C roast 4 hours.Above-mentioned catalyst is cut into 1-3mm, cylindrical catalyst parent is made
F0.20 grams of precursor catalyst F0 is added to the aqueous citric acid solution of 150ml weight content 0.5mol/L, 80 DEG C are impregnated 4 hours.
120 DEG C of drying, 500 DEG C of roastings, 2 hours obtained F1.Use concentration for the calcium nitrate aqueous solution of 18 weight % in 20 grams of F1 sample
Dipping 24 hours, 120 DEG C of drying, 700 DEG C roast 3 hours, and calcium oxide weight content is 10%, and F2 is made.20 grams of F2 are existed
It is carried out steam treatment 10 hours in 100% steam atmosphere, treatment temperature is 350 DEG C, and 550 DEG C are made catalysis in roasting 3 hours
Agent F.The content that molecular sieve in catalyst is made is 80%.
Embodiment 5
The preparation process of catalyst is as follows: the 200 grams and 125 grams packets of ammonia type ZSM-5 molecular sieve for being 40 by mole silica alumina ratio
Silica solution mixing containing the silica that weight percent is 40%, be added suitable 10% dust technology as extrusion aid extrusion at
Type.120 DEG C of drying, 550 DEG C roast 4 hours.Above-mentioned catalyst is cut into 1-3mm, cylindrical catalyst parent G0 is made.By 20 grams
Precursor catalyst G0 be added 50ml weight content 0.5mol/L oxalic acid aqueous solution, 80 DEG C impregnate 12 hours.120 DEG C of drying,
500 DEG C of roastings, 2 hours obtained G1.Use concentration small for the barium nitrate aqueous solution of 10 weight % dipping 36 in 20 grams of G1 sample
When, 120 DEG C of drying, 700 DEG C roast 3 hours, and barium monoxide weight content is 10%, and G2 is made.By 20 grams of G2 in 100% vapor
It is carried out steam treatment 10 hours in atmosphere, treatment temperature is 450 DEG C, 550 DEG C of roastings, 3 hours obtained catalyst G.Catalysis is made
The content of molecular sieve is 80% in agent.
Embodiment 6
The preparation process of catalyst is as follows: the 140 grams and 20 grams oxidations of ammonia type ZSM-5 molecular sieve for being 30 by mole silica alumina ratio
Silicon, 100 grams of silica solution comprising the silica that weight percent is 40% mix, and suitable 10% dust technology of addition, which is used as, to be helped
Squeeze agent extruded moulding.120 DEG C of drying, 550 DEG C roast 4 hours.Above-mentioned catalyst is cut into 1-3mm, cylindrical catalyst parent is made
H0.Concentration is used to impregnate 20 hours for the barium nitrate aqueous solution of 2 weight % in 20 grams of H2 sample, 120 DEG C of drying, 700 DEG C of roastings
It burns 3 hours, barium monoxide weight content is 2%, and H2 is made.20 grams of H3 are subjected to steam treatment 4 in 100% steam atmosphere
Hour, treatment temperature is 550 DEG C, 550 DEG C of roastings, 3 hours obtained catalyst H.The content of molecular sieve is in obtained catalyst
70%.
Embodiment 7
The preparation process of catalyst is as follows: 170 grams of the HZSM-5 molecular sieve that mole silica alumina ratio is 30 is included weight with 100 grams
The silica solution mixing for measuring the silica that percentage is 30%, is added suitable 10% dust technology as extrusion aid extruded moulding.
120 DEG C of drying, 550 DEG C roast 4 hours.Above-mentioned catalyst is cut into 1-3mm, cylindrical catalyst parent I0 is made.By 20 grams of I0
Sample uses concentration to impregnate 20 hours for the magnesium acetate aqueous solution of 14 weight %, and 120 DEG C of drying, 700 DEG C roast 3 hours, oxidation
Magnesium weight content is 6%, and I1 is made.20 grams of I1 are carried out steam treatment 10 hours in 100% steam atmosphere, processing temperature
Degree is 350 DEG C, 550 DEG C of roastings, 3 hours obtained catalyst I.The content that molecular sieve in catalyst is made is 85%.
Embodiment 8
The preparation process of catalyst is as follows: 160 grams of the HZSM-5 molecular sieve that mole silica alumina ratio is 20 is included weight with 100 grams
The silica solution mixing for measuring the silica that percentage is 40%, is added suitable 10% dust technology as extrusion aid extruded moulding.
120 DEG C of drying, 550 DEG C roast 4 hours.Above-mentioned catalyst is cut into 1-3mm, cylindrical catalyst parent J0 is made.By 20 grams of J0
Sample uses concentration to impregnate 24 hours for the iron nitrate aqueous solution of 20 weight %, and 120 DEG C of drying, 700 DEG C roast 3 hours, oxidation
Iron weight content is 10%, and J1 is made.20 grams of J1 are carried out steam treatment 4 hours in 100% steam atmosphere, processing temperature
Degree is 350 DEG C, 550 DEG C of roastings, 3 hours obtained catalyst J.The content that molecular sieve in catalyst is made is 80%.
Embodiment 9
The preparation process of catalyst is as follows: 160 grams of the HZSM-5 molecular sieve that mole silica alumina ratio is 30 is included weight with 100 grams
The silica solution mixing for measuring the silica that percentage is 40%, is added suitable 10% dust technology as extrusion aid extruded moulding.
120 DEG C of drying, 550 DEG C roast 4 hours.Above-mentioned catalyst is cut into 1-3mm, cylindrical catalyst parent K0 is made.By 20 grams of K0
Sample uses concentration to impregnate 24 hours for the nickel nitrate aqueous solution of 7.8 weight %, and 120 DEG C of drying, 600 DEG C roast 3 hours, oxidation
Nickel weight content is 3%, and K1 is made.20 grams of K1 are carried out steam treatment 4 hours in 100% steam atmosphere, processing temperature
Degree is 350 DEG C, 550 DEG C of roastings, 3 hours obtained catalyst K.The content that molecular sieve in catalyst is made is 80%.
Embodiment 10
The preparation process of catalyst is as follows: 160 grams of the HZSM-5 molecular sieve and 40 grams of diatomite for being 30 by mole silica alumina ratio
Suitable 10% dust technology is added as extrusion aid extruded moulding in mixing.120 DEG C of drying, 550 DEG C roast 4 hours.By 20 grams
L0 sample uses concentration to impregnate 24 hours for the magnesium nitrate aqueous solution of 25 weight %, and 120 DEG C of drying, 600 DEG C roast 3 hours, oxygen
Changing magnesium weight content is 10%, and L1 is made.20 grams of L1 are carried out steam treatment 2 hours in 100% steam atmosphere, are handled
Temperature is 600 DEG C, 550 DEG C of roastings, 3 hours obtained catalyst L.The content that molecular sieve in catalyst is made is 80%.
Embodiment 11
The preparation process of catalyst is as follows: be 170 grams of HMCM-22 molecular sieve of 20 for mole silica alumina ratio includes with 100 grams
The silica solution mixing for the silica that weight percent is 30%, be added suitable 10% dust technology as extrusion aid extrusion at
Type.120 DEG C of drying, 550 DEG C roast 4 hours.Above-mentioned catalyst is cut into 1-3mm, cylindrical catalyst parent M0 is made.By 20 grams
M0 sample use concentration for the mixed aqueous solution of the barium nitrate of 5 weight % and the magnesium nitrate of 12.5 weight % dipping 10 hours,
120 DEG C of drying, 700 DEG C roast 3 hours, barium monoxide content 5%, and magnesia weight content is 5%, and M1 is made.20 grams of M1 are existed
It is carried out steam treatment 10 hours in 100% steam atmosphere, treatment temperature is 450 DEG C, and 550 DEG C are made catalysis in roasting 3 hours
Agent M.The content that molecular sieve in catalyst is made is 85%.
Embodiment 12
The preparation process of catalyst is as follows: be 170 grams of HMCM-22 molecular sieve of 60 for mole silica alumina ratio includes with 100 grams
The silica solution mixing for the silica that weight percent is 30%, be added suitable 10% dust technology as extrusion aid extrusion at
Type.120 DEG C of drying, 550 DEG C roast 4 hours.Above-mentioned catalyst is cut into 1-3mm, cylindrical catalyst parent N0 is made.By 20 grams
N2 sample use concentration for the mixed aqueous solution of the calcium acetate of 5.7 weight % and the magnesium acetate of 7 weight % dipping 10 hours,
120 DEG C dry, and roast 3 hours at 650 DEG C, and calcium oxide weight content is 3%, and magnesia weight content is 3%, and N1 is made.It will
20 grams of N1 are carried out steam treatment 10 hours in 100% steam atmosphere, and treatment temperature is that roasting 3 is small at 350 DEG C, 550 DEG C
When be made catalyst n.The content that molecular sieve in catalyst is made is 85%.
Embodiment 13
The preparation process of catalyst is as follows: be 170 grams of HMCM-22 molecular sieve of 50 for mole silica alumina ratio includes with 100 grams
The silica solution mixing for the silica that weight percent is 30%, be added suitable 10% dust technology as extrusion aid extrusion at
Type.120 DEG C of drying, 550 DEG C roast 4 hours.Above-mentioned catalyst is cut into 1-3mm, cylindrical catalyst parent P0 is made.By 20 grams
P2 sample use concentration for 3 weight % barium nitrate aqueous solution soak 36 hours, 120 DEG C drying, 700 DEG C roast 3 hours, oxidation
Barium weight content is 3%, and P1 is made.20 grams of P1 are carried out steam treatment 10 hours in 100% steam atmosphere, processing temperature
Degree is 350 DEG C, 550 DEG C of roastings, 3 hours obtained catalyst P.The content that molecular sieve in catalyst is made is 85%.
Embodiment 14
The preparation process of catalyst is as follows: being 40 80 grams of HMCM-22 molecular sieve and 100 grams of diatoms by mole silica alumina ratio
Native, 100 grams of silica solution comprising the silica that weight percent is 20% mix, and suitable 10% dust technology of addition, which is used as, to be helped
Squeeze agent extruded moulding.120 DEG C of drying, 550 DEG C roast 4 hours.Above-mentioned catalyst is cut into 1-3mm, cylindrical catalyst parent is made
R0.Concentration is used to impregnate 20 hours for the iron nitrate solution of 6 weight % in 20 grams of R0 sample, 120 DEG C of drying, 700 DEG C of roastings 3
Hour, iron oxide weight content is 3%, and R1 is made.It is small that 20 grams of R1 are carried out to steam treatment 6 in 100% steam atmosphere
When, treatment temperature is 350 DEG C, 550 DEG C of roastings, 3 hours obtained catalyst R.The content that molecular sieve in catalyst is made is 40%.
Embodiment 15
The preparation process of catalyst is as follows: mole silica alumina ratio is included weight for 20 170 grams of beta molecular sieve and 100ml
The silica solution mixing for the silica that percentage is 30%, is added suitable 10% dust technology as extrusion aid extruded moulding.120
DEG C drying, 550 DEG C roast 4 hours.Above-mentioned catalyst is cut into 1-3mm, cylindrical catalyst parent S0 is made.By 20 grams of S0 sample
Product use concentration to impregnate 20 hours for the calcium acetate aqueous solution of 2 weight %, and 120 DEG C of drying, 700 DEG C roast 3 hours, calcium oxide weight
Measuring content is 1%, and S1 is made.20 grams of S1 are carried out steam treatment 4 hours in 100% steam atmosphere, treatment temperature is
3 hours obtained catalyst S are roasted at 550 DEG C, 550 DEG C.The content that molecular sieve in catalyst is made is 85%.
Embodiment 16
The preparation process of catalyst is as follows: 60 grams of the HMCM-22 molecular sieve that mole silica alumina ratio is 30 is included weight with 100 grams
The silica solution for the silica that percentage is 40% is measured, it is crowded as helping that suitable 10% dust technology is added in 100 grams of aluminium oxide mixing
Agent extruded moulding.120 DEG C of drying, 550 DEG C roast 4 hours.Above-mentioned catalyst is cut into 1-3mm, cylindrical catalyst parent is made
T0.Concentration is used to impregnate 20 hours for the nickel nitrate aqueous solution of 2.6 weight % in 20 grams of T0 sample, 120 DEG C of drying, 700 DEG C
Roasting 3 hours, nickel oxide weight content are 1%, and T1 is made.20 grams of T1 are carried out at vapor in 100% steam atmosphere
Reason 4 hours, treatment temperature are to roast 3 hours obtained catalyst T at 550 DEG C, 550 DEG C.The content of molecular sieve in catalyst is made
It is 30%.
Embodiment 17
By catalyst made from embodiment 1-16, the reaction of o-cresol methanol etherification is carried out on fixed-bed reactor.It is former
Material o-cresol, methanol and the preheated reactor that enters of vapor are reacted, the analysis of reaction product on-line chromatograph.Gas-chromatography is
Agilent 7890A, chromatographic column are 0.25 μm of X of cyclodextrin column 30m X 0.25mm.Chromatographiccondition: column temperature: initial temperature 150
DEG C, it stops 15 minutes, 10 DEG C/min of heating rates rise to 180 DEG C, constant temperature 5.3 minutes；Carrier gas is high pure nitrogen, is pressed before column:
6.5pisa, column flow rate 12.6cm/sec.Catalysts loadings are 20.0 grams, weight space velocity 0.5-20 hours-1, reaction temperature
250-500 DEG C of degree, carrier gas are vapor, and the molar ratio of carrier gas and o-cresol is 0.5-20. raw material o-cresol and methanol
Molar ratio is 1: 10 to 1: 3.72 hours reaction results of catalyst reaction are listed in table 1 in various embodiments.
1 reaction condition of table and reaction result
Embodiment 18-21
Catalyst test apparatus is identical as embodiment 17 as test method.Catalysts loadings are 20.0 grams, charging
The molar ratio of methanol and o-cresol be 5: 1, weight space velocity 3 hours-1, carrier gas is vapor or nitrogen, and carrier gas and charging are adjacent
The molar ratio of cresols is 6.The reaction result of catalyst is listed in table 2 in various embodiments.
The reactivity worth of 2 catalyst of table
By the result of above embodiments 1-21 it is found that the catalyst prepared according to the technique and scheme of the present invention is with good
Stability is a kind of environmental-friendly catalyst.In addition, passing through by using the catalyst using o-cresol and methanol as raw material
Higher o-cresol conversion ratio and o-methoxy toluene selectivity may be implemented in the method for etherification reaction production o-methoxy toluene.
Embodiment of the present invention is only the description carried out to the preferred embodiment of the present invention, not to the present invention
Conception and scope be defined, under the premise of not departing from design philosophy of the present invention, in this field engineers and technicians to this
The all variations and modifications that the technical solution of invention is made, should all fall into protection scope of the present invention, and the present invention is claimed
Technology contents are all described in the claims.
Claims (18)
1. a kind of preparation method of catalyst for etherification, which comprises
A) it is roasted 4 to 10 hours by molecular sieve and binder mixed-forming and at 500 to 700 DEG C；
C) oxide modifying is carried out to product obtained in previous step and is roasted 3 to 10 hours at 550 to 700 DEG C, wherein
The oxide is selected from one of alkaline earth oxide and transition metal oxide or a variety of；With
D) to product obtained in previous step 300 to 800 DEG C progress steam treatment 0.5 to 10 hour,
Wherein the implementation sequence of step c) and step d) can be interchanged.
2. the preparation method of catalyst for etherification according to claim 1, the method also includes the following of follows step a)
Step b):
B) sour processing is carried out to product obtained in step a) and is roasted 2 to 10 hours at 500 to 600 DEG C.
3. the preparation method of catalyst for etherification according to claim 1, wherein the molecular sieve be selected from ZSM-5 molecular sieve,
One of MCM-22 molecular sieve and BETA molecular sieve are a variety of.
4. the preparation method of catalyst for etherification according to claim 3, wherein the silica alumina ratio of the molecular sieve is 20:
1 to 80: 1.
5. the preparation method of catalyst for etherification according to claim 3, wherein the molecular sieve is hydrogen type molecular sieve or ammonium
Type molecular sieve.
6. the preparation method of catalyst for etherification according to claim 1, wherein the binder is selected from silica solution, diatomite
One or more of with silica.
7. the preparation method of catalyst for etherification according to claim 6, wherein the total weight based on the silica solution, described
Silica solution includes the silica that weight percent is 20%-40%.
8. the preparation method of catalyst for etherification according to claim 1, wherein in step a), the molecular sieve with it is described
The weight ratio of binder is 30: 70 to 85: 15.
9. the preparation method of catalyst for etherification according to claim 1, wherein the alkaline-earth metal is in calcium, magnesium and barium
It is one or more, and the alkaline earth oxide is selected from one of calcium oxide, magnesia and barium monoxide or a variety of；Institute
It states transition metal and is selected from one of iron and nickel or a variety of, and the transition metal oxide is in iron oxide and nickel oxide
It is one or more.
10. the preparation method of catalyst for etherification according to claim 9, wherein the oxide modifying includes: by upper one
The product that step obtains impregnates in the acid salt of the alkaline-earth metal or the acid salt of the transition metal and then makes
The acid salt thermal decomposition of the acid salt or the transition metal of the alkaline-earth metal impregnated in products therefrom, to generate the alkali
Soil metal oxide or the transition metal oxide.
11. the preparation method of catalyst for etherification according to claim 1, wherein when the modification for carrying out alkaline earth oxide
When, it is based on the total weight of product obtained in step c), the content of the alkaline earth oxide in product obtained in step c)
For 0.1 to 10 weight %.
12. the preparation method of catalyst for etherification according to claim 1, wherein when the modification for carrying out transition metal oxide
When, it is based on the total weight of product obtained in step c), the content of the transition metal oxide in product obtained in step c)
For 0.1 to 10 weight %.
13. the preparation method of catalyst for etherification according to claim 1, wherein the steam treatment is saturated steam
Processing.
14. the preparation method of catalyst for etherification according to claim 2, wherein the acid processing includes that will obtain in step a)
The product arrived normal temperature dipping 4 to 24 hours in mineral acid, or by product obtained in step a) in organic acid 30 to
80 DEG C impregnate 4 to 12 hours.
15. the preparation method of catalyst for etherification according to claim 14, wherein the inorganic acid is selected from nitric acid and sulfuric acid
One of or it is a variety of, and the organic acid be selected from one of citric acid and oxalic acid or a variety of.
16. a kind of method for producing o-methoxy toluene by etherification reaction as raw material using o-cresol and methanol, the method packet
It includes: in 250 to 500 DEG C of reaction temperatures, 0.5 to 20h-1Feed weight air speed and condition of normal pressure under, by o-cresol, methanol
The catalyst bed of catalyst for etherification is mixed and had by load with carrier gas, and the catalyst for etherification is by according to right
It is required that the preparation of preparation method described in any one of 1 to 15.
17. the method according to claim 16 that o-methoxy toluene is produced by etherification reaction from o-cresol and methanol,
Wherein the carrier gas is nitrogen or vapor.
18. the method according to claim 16 that o-methoxy toluene is produced by etherification reaction from o-cresol and methanol,
Wherein the molar ratio of o-cresol and methanol is 1: 10 to 1: 3, and the molar ratio of the carrier gas and o-cresol is 0.5: 1 to 20
∶1。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710595153.9A CN109277115A (en) | 2017-07-19 | 2017-07-19 | The preparation method of catalyst for etherification and the method for producing o-methoxy toluene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710595153.9A CN109277115A (en) | 2017-07-19 | 2017-07-19 | The preparation method of catalyst for etherification and the method for producing o-methoxy toluene |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109277115A true CN109277115A (en) | 2019-01-29 |
Family
ID=65184330
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710595153.9A Pending CN109277115A (en) | 2017-07-19 | 2017-07-19 | The preparation method of catalyst for etherification and the method for producing o-methoxy toluene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109277115A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109809970A (en) * | 2019-02-01 | 2019-05-28 | 宝鸡文理学院 | A kind of method of catalysis of phenol and methanol production methyl phenyl ethers anisole |
| CN109879730A (en) * | 2019-02-01 | 2019-06-14 | 宝鸡文理学院 | A kind of method of phenol and methanol production methyl phenyl ethers anisole |
| CN109879727A (en) * | 2019-02-01 | 2019-06-14 | 宝鸡文理学院 | A kind of method of phenol and methanol-fueled CLC methyl phenyl ethers anisole |
| CN109879728A (en) * | 2019-02-01 | 2019-06-14 | 宝鸡文理学院 | A kind of method of catalysis of phenol and methanol-fueled CLC methyl phenyl ethers anisole |
| CN112521241A (en) * | 2019-09-19 | 2021-03-19 | 中国科学院大连化学物理研究所 | Method for preparing durene from carbon monoxide and methanol |
| CN113413893A (en) * | 2021-07-28 | 2021-09-21 | 中榕盛煜能源科技股份有限公司 | Ether-based catalyst and preparation method thereof |
| WO2023232235A1 (en) * | 2022-05-31 | 2023-12-07 | Symrise Ag | 1-(methoxymethyl)-2-methyl-benzene as a fragrance |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS577432A (en) * | 1980-06-16 | 1982-01-14 | Nippon Gosei Arukoole Kk | Preparation of dialkyl ether |
| CN1267277A (en) * | 1997-07-09 | 2000-09-20 | 罗狄亚化学公司 | Method for etherifying benzyl alcohol, resulting products and applications |
| JP2001335523A (en) * | 2000-05-31 | 2001-12-04 | Sumitomo Chem Co Ltd | Method for o-alkylation of phenol |
| JP2004182631A (en) * | 2002-12-02 | 2004-07-02 | Nippon Shokubai Co Ltd | Method for producing alkyl phenyl ethers |
| CN103288602A (en) * | 2012-02-23 | 2013-09-11 | 中国科学院大连化学物理研究所 | Method for preparing p-cresol from anisole and preparation method of used catalyst thereof |
| CN103570505A (en) * | 2012-07-24 | 2014-02-12 | 中国科学院大连化学物理研究所 | Method of producing methylphenol by using molecular sieve as catalyst |
| CN103570504A (en) * | 2012-07-24 | 2014-02-12 | 中国科学院大连化学物理研究所 | Method of producing methylphenol by gas-phase alkylation of phenol and methanol |
| CN106215959A (en) * | 2016-07-21 | 2016-12-14 | 河北旻灏科技有限公司 | A kind of O alkylation produces aromatic ether special-purpose catalyst and the method producing aromatic ether |
-
2017
- 2017-07-19 CN CN201710595153.9A patent/CN109277115A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS577432A (en) * | 1980-06-16 | 1982-01-14 | Nippon Gosei Arukoole Kk | Preparation of dialkyl ether |
| CN1267277A (en) * | 1997-07-09 | 2000-09-20 | 罗狄亚化学公司 | Method for etherifying benzyl alcohol, resulting products and applications |
| JP2001335523A (en) * | 2000-05-31 | 2001-12-04 | Sumitomo Chem Co Ltd | Method for o-alkylation of phenol |
| JP2004182631A (en) * | 2002-12-02 | 2004-07-02 | Nippon Shokubai Co Ltd | Method for producing alkyl phenyl ethers |
| CN103288602A (en) * | 2012-02-23 | 2013-09-11 | 中国科学院大连化学物理研究所 | Method for preparing p-cresol from anisole and preparation method of used catalyst thereof |
| CN103570505A (en) * | 2012-07-24 | 2014-02-12 | 中国科学院大连化学物理研究所 | Method of producing methylphenol by using molecular sieve as catalyst |
| CN103570504A (en) * | 2012-07-24 | 2014-02-12 | 中国科学院大连化学物理研究所 | Method of producing methylphenol by gas-phase alkylation of phenol and methanol |
| CN106215959A (en) * | 2016-07-21 | 2016-12-14 | 河北旻灏科技有限公司 | A kind of O alkylation produces aromatic ether special-purpose catalyst and the method producing aromatic ether |
Non-Patent Citations (2)
| Title |
|---|
| M.E.SAD等: "Study of the phenol methylation mechanism on zeolites HBEA, HZSM5 and HMCM22", 《JOURNAL OF MOLECULAR CATALYSIS A: CHEMICAL》 * |
| 王利军: "苯酚与甲醇合成苯甲醚沸石催化剂的研究", 《石油学报(石油加工)》 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109809970A (en) * | 2019-02-01 | 2019-05-28 | 宝鸡文理学院 | A kind of method of catalysis of phenol and methanol production methyl phenyl ethers anisole |
| CN109879730A (en) * | 2019-02-01 | 2019-06-14 | 宝鸡文理学院 | A kind of method of phenol and methanol production methyl phenyl ethers anisole |
| CN109879727A (en) * | 2019-02-01 | 2019-06-14 | 宝鸡文理学院 | A kind of method of phenol and methanol-fueled CLC methyl phenyl ethers anisole |
| CN109879728A (en) * | 2019-02-01 | 2019-06-14 | 宝鸡文理学院 | A kind of method of catalysis of phenol and methanol-fueled CLC methyl phenyl ethers anisole |
| CN109879727B (en) * | 2019-02-01 | 2022-04-19 | 宝鸡文理学院 | Method for synthesizing anisole from phenol and methanol |
| CN109879730B (en) * | 2019-02-01 | 2022-04-19 | 宝鸡文理学院 | Method for producing anisole from phenol and methanol |
| CN112521241A (en) * | 2019-09-19 | 2021-03-19 | 中国科学院大连化学物理研究所 | Method for preparing durene from carbon monoxide and methanol |
| CN112521241B (en) * | 2019-09-19 | 2022-06-21 | 中国科学院大连化学物理研究所 | Method for preparing durene from carbon monoxide and methanol |
| CN113413893A (en) * | 2021-07-28 | 2021-09-21 | 中榕盛煜能源科技股份有限公司 | Ether-based catalyst and preparation method thereof |
| WO2023232235A1 (en) * | 2022-05-31 | 2023-12-07 | Symrise Ag | 1-(methoxymethyl)-2-methyl-benzene as a fragrance |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109277115A (en) | The preparation method of catalyst for etherification and the method for producing o-methoxy toluene | |
| CN109277113A (en) | The preparation method of catalyst for etherification and the method for producing methylanisole | |
| CN103570504B (en) | The method of cresols is produced in a kind of phenol methanol vapor phase alkylation | |
| CN109277114A (en) | The preparation method of catalyst for etherification and the method for producing methyl phenyl ethers anisole | |
| CN103570505B (en) | A kind of take molecular sieve as the method for Catalyst Production cresols | |
| CN103464193B (en) | Fluidized catalyst for alcohol ether and hydrocarbon aromatization, and preparation method and application method thereof | |
| WO2014101374A1 (en) | A process for the production of cresol | |
| CN103664440B (en) | Methanol conversion produces the method for aromatic hydrocarbons | |
| CN104190391A (en) | Catalyst and application of catalyst to method for preparing thymol | |
| CN104117385A (en) | Modified IM-5 molecular sieve and catalyst as well as application | |
| CN106694029A (en) | Nonmetal modified catalyst and preparation method for same | |
| CN106622335B (en) | For Benzyl Side-Chain alkylated reaction preparation of styrene and the catalyst of ethylbenzene and application thereof | |
| CN105964293A (en) | Molecular sieve based catalyst for directly preparing polymethyl benzene and preparation and usage methods thereof | |
| CN110227546B (en) | Catalyst for preparing p-xylene by methanol conversion and preparation method thereof | |
| CN109942383A (en) | A kind of method of mixed phenol methanol vapor phase etherificate production compound ether | |
| CN107899609B (en) | Catalyst for producing polyformaldehyde dimethyl ether and preparation method thereof | |
| CN103288602B (en) | Method for preparing p-cresol from anisole and preparation method of used catalyst thereof | |
| CN104437596B (en) | Methanol arenes catalytic agent and preparation method thereof | |
| CN102173977A (en) | Cu/Al2O3 catalyst and preparation method thereof as well as method for catalyzing hydrolysis of glycerol | |
| CN102371178A (en) | Catalyst for preparing arene by methanol conversion and preparation method thereof | |
| CN105983434A (en) | Preparation method and use of binder-free ZSM-11 molecular sieve-based catalyst | |
| CN112521967B (en) | Method for preparing mixed aromatic hydrocarbon from carbon monoxide and methanol | |
| CN104557427A (en) | Method for preparing aromatic hydrocarbon from oxygenated chemicals | |
| CN104549444A (en) | Catalyst for preparing aromatic hydrocarbon from oxygen-containing compound | |
| CN105061154A (en) | Method for continuously preparing thymol |
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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190129 |
|
| RJ01 | Rejection of invention patent application after publication |