CN110204444A - Synthesis method of dimethyl carbonate - Google Patents
Synthesis method of dimethyl carbonate Download PDFInfo
- Publication number
- CN110204444A CN110204444A CN201910590296.XA CN201910590296A CN110204444A CN 110204444 A CN110204444 A CN 110204444A CN 201910590296 A CN201910590296 A CN 201910590296A CN 110204444 A CN110204444 A CN 110204444A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- production technology
- technology according
- carrier
- koh
- 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.)
- Granted
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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/843—Arsenic, antimony or bismuth
- B01J23/8437—Bismuth
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C68/00—Preparation of esters of carbonic or haloformic acids
- C07C68/06—Preparation of esters of carbonic or haloformic acids from organic carbonates
- C07C68/065—Preparation of esters of carbonic or haloformic acids from organic carbonates from alkylene carbonates
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to the field of production processes of chemical raw materials, and particularly relates to a production process for synthesizing dimethyl carbonate by using an ester exchange method. The catalyst used in the production process consists of 6-10 wt% of active component and the balance of carrier, wherein the active component is Bi2O3And KOH, Bi2O3: KOH (weight ratio) 1: 2-4; the carrier is zinc-iron composite metal oxide. The production process for synthesizing the dimethyl carbonate has the advantages of mild reaction conditions, lower production cost and high yield of the dimethyl carbonate.
Description
Technical field
The invention belongs to the production technology fields of industrial chemicals, and in particular to one kind passes through ester-interchange method carbonate synthesis diformazan
The production technology of ester.
Background technique
Dimethyl carbonate (dimethyl carbonate, abbreviation DMC) be in recent years quite valued one kind it is widely used,
Meet the environment-friendly type Organic Chemicals that modern " cleaning procedure " requires, is known as " the new matrix " of organic synthesis.Due to its point
Contain methoxyl group, carbonyl and carbonyl methyl in son, there is hypotoxicity, highly dissoluble, excellent environmental-protecting performance and reaction work well
Property, it may replace hypertoxic phosgene and dimethyl suflfate, be widely used in carbonylation and methylating reagent, gasoline additive, synthesis gather
The fast development industry such as raw material, paint solvent and lithium battery electrolytes of carbonic ester, has broad mass market, is current chemical industry neck
The green chemical of domain hot topic.
The industrial process of dimethyl carbonate has light phosgenation, methanol liquid-phase oxidative carbonylation method and ester-interchange method.Its
Middle ester-interchange method because its reaction condition is mild, process flow is simple, equipment cost is low, coproduction alkane glycol due to be paid more and more attention,
Method as current great prospects for commercial application.Ester-interchange method synthesis of dialkyl carbonates used catalyst mainly has homogeneous alkali
Catalyst, such as triethylamine, triphenyl phasphine and solid base catalyst are generally the hydroxide, alkoxide or carbonic acid of alkali metal
Salt, such as sodium hydroxide, potassium hydroxide, sodium methoxide and potassium carbonate.Homogeneous catalyst activity is high, but is not readily separated, and is unfavorable for industry
Change.Compared with homogeneous base catalyst, solid base catalyst has many advantages, such as not corrode that equipment, environmental pollution is small, is easily recycled, and is
The most catalyst system of development prospect in the reaction of ester-interchange method synthesis of dialkyl carbonates.
One kind as disclosed in Chinese patent CN102471221A is comprising that can generate hydrogen ion (H+) cation and contain
The ionic liquid of fluorine hydrophobic anion, and it is selected from alkaline earth oxide, transition metal oxide, rare earth oxide and neatly
In the presence of the catalyst of at least one of stone, is reacted by alkylol with urea or alkyl carbamate and prepare dialkyl group
The method of carbonic ester.Although this method can improve business efficiency to prepare dialkyl carbonate in high yield, used
Catalysis agent producing process is more complicated, and production cost is higher.
If Chinese patent CN107096540A discloses a kind of technique for alcoholysis of urea Synthesis of dimethyl carbonate,
Used in metallic element in metal composite oxide contained in catalyst include following four: Mg2+、Sn2+、Ni2+With
Al3+.Houghite precursor is first made by coprecipitation in it, and then roasting obtains.Catalyst is anti-at 200 DEG C in the process
At a temperature of answering, the yield of DMC reaches as high as 55.3%.
If Chinese patent CN105879892A discloses a kind of synthesis of dimethyl carbonate via transesterification production technology, used in
The group of solid base catalyst become Ca-Al-O-X, the molar content of Ca is 15-35%, and the molar content of Al is 5-30%, X
Molar content be 0.1%-10%, remaining be O content.The reaction temperature of the technique is lower, is 60 DEG C, the yield of DMC is most
It is high by reachable 55.7%.
If Chinese patent CN109772286A discloses a kind of production technology by ester-interchange method carbonate synthesis Arrcostab,
Solid base catalyst used in it includes the active component sodium aluminate of carrier and load on the carrier；The carrier is choosing
From the compound of at least one of zinc-aluminium metal composite oxide, nickel aluminum composite metal oxide, cobalt-aluminum composite metal oxide
Metal oxide.Its preparation process includes: the houghite precursor for preparing the metal composite oxide first, then impregnates aluminium
Sour sodium, roasting, obtains the solid base catalyst.Under 65 DEG C of reaction temperature, the yield of DMC reaches as high as the catalyst
75.1%.
If United States Patent (USP) US4691041A discloses a kind of production technology of Synthesis of dimethyl carbonate, used in it is non-
Phase catalyst is selected from the ion exchange resin with quaternary ammonium functional group, the ion exchange resin with sulfonate functional groups, band carboxylic acid group
The molecular sieve that the ion exchange resin of functional group, the silica for being impregnated with alkali/alkaline earth metal silicate, ammonium exchange.The technique exists
Under 100 DEG C of reaction temperature, the yield of DMC reaches as high as 23.7%.
In general, in the production technology of existing Synthesis of dimethyl carbonate ester-interchange method due to reaction condition it is mild etc. excellent
It puts and becomes the production technology for most having application prospect.But the catalytic of the catalyst for synthesis of dimethyl carbonate via transesterification
Various shortcomings can be still had, therefore need to develop performance of new generation more preferably catalyst with the industry to dimethyl carbonate
Production provides more favorable supporting function.
Summary of the invention
For this purpose, technical problems to be solved in this application are how to provide a kind of high income of dimethyl carbonate, reaction
Mild condition, the production technology of the Synthesis of dimethyl carbonate of lower production costs.
In order to solve the above technical problems, present inventor is by the research conscientiously with effort, it was found that pass through application
A kind of high performance catalyst can solve the above technical problem.Firstly, producing the hydrotalcite precursor of carrier using coprecipitation；
Then, in the case of not being fired, directly by wet impregnation come load active component bismuth oxide (Bi2O3) and potassium hydroxide
(KOH), then dry, roasting can be prepared by the height that zinc-iron metal composite oxide loads the active component under optimum conditions
Performance catalyst.ZnO and ZnFe in the carrier of the catalyst2O4With suitable ratio and interaction force, active component point
Cloth is uniform, and the interaction force between active component and carrier is moderate.
Technical scheme is as follows: the invention discloses a kind of productions by synthesis of dimethyl carbonate via transesterification
Technique, used in catalyst be made of the active component of 6-10wt% and the carrier of surplus, the active component be Bi2O3
And KOH, Bi2O3: KOH (weight ratio)=1:2-4；The carrier is zinc-iron metal composite oxide.
The content of the active component is preferably 6-8wt%, based on the total catalyst weight.
Carrier in the application catalyst is roasted by houghite precursor to be made, general formula are as follows: [Zn2+ 1-xFe3+ x(OH)2]x+
(CO3 2-)x/2·nH2O, wherein 0.2≤x≤0.33,1≤n≤10.
X in the general formula is more preferably 0.25≤x≤0.33, most preferably x=0.25.
Present inventor it has been investigated that, in catalyst used herein, pass through selection specific composition zinc
Precursor of the molten iron talcum as carrier, under unfired situation, load active component, then control is dry and roasts item
Part can make ZnO and ZnFe in carrier2O4Exist with suitable ratio, without will lead to ZnO or ZnFe2O4Excessively, no matter both
In it is any excessive, can all cause catalytic activity significant decline occur, and can make between both components in carrier
With suitable interaction force, while it can also make that also there is very moderate active force between active component and carrier, thus
The low temperature active and stability for substantially increasing catalyst, extend the service life of catalyst.
, whereas if being made after houghite precursor, first roasting is (after roasting condition and the application load active component
Roasting condition it is identical) obtain zinc-iron composite oxides, recycle the present processes load active component, then identical anti-
Test catalyst performance under the conditions of answering, it is found that the conversion ratio of the ethylene carbonate of the catalyst is only 62.8%, and its
When the 5th reuses, catalytic activity, which occurs as soon as, to be decreased obviously, and catalytic performance on the whole will be much worse than the catalysis of the application
Agent.Its reason is analyzed, very big may be carrier experience double roasting, so that ZnFe therein2O4Content is crossed to obviously increase, and
And also greatly affected the active force between active component and carrier, cause active component to be easy inactivation.
It also found through research, the carrier and active component Bi2O3And KOH, collaboration beyond expectation is produced between three
Effect makes catalyst have very high low-temperature catalytic activity.Although composition metal made from KOH known in the art or hydrotalcite
Oxide can be directly used as the catalyst of Synthesis of dimethyl carbonate, but not about the composition metal made from zinc-iron hydrotalcite
Oxide is used as the catalyst of Synthesis of dimethyl carbonate or the report of carrier, also not about Bi2O3It can be used as the synthesis of KOH base
The report of the auxiliary agent of catalyst.Catalyst performance is tested under identical reaction conditions, individually with KOH, Bi2O3、
When metal composite oxide is as catalyst, highest catalytic activity is KOH catalyst, but the conversion ratio of its ethylene carbonate is only
It is 41%, is still much lower than the catalyst of the application.
The invention also discloses the preparation methods of the catalyst, include the following steps:
1) first, in accordance with the composition of final carrier, houghite precursor is made；
2) composition for pressing final catalyst, weighs KOH, soluble bismuth salt, deionized water is added to be configured to maceration extract；
3) in the maceration extract made from step 2), the obtained houghite precursor of step 1) is added, carries out wet impregnation
(i.e. excess solution impregnation method)；Then filter cake is filtered or be centrifugally separating to obtain, is washed；
4) filter cake is freeze-dried, then under air atmosphere, roasts 3-8h at 400-550 DEG C, is subsequently reduced to room temperature, i.e.,
Catalyst prod can be made.
Soluble bismuth salt in step 2) is selected from one of bismuth nitrate, bismuth acetate, cobaltous sulfate, cobalt chloride etc. or a variety of,
Preferably bismuth nitrate.
Bismuth concentration is 0.1-1mol/L, more preferably 0.3-0.7mol/L in maceration extract in step 2)；KOH concentration is
0.5-2mol/L, more preferably 1-1.5mol/L.
The detailed process of the freeze-drying of step 3) are as follows: first filter cake is placed in freezing chamber and is frozen into solid, is then existed
So that steam is distilled under reduced pressure, obtains desciccate.
The roasting process of step 4) is preferred are as follows: by desciccate with the heating rate of 5-15 DEG C/min by room temperature extremely
200-250 DEG C, 1-2h is kept the temperature, then proceedes to be warming up to 400-550 DEG C, more preferably 450- with the heating rate of 5-15 DEG C/min
500 DEG C, and 3-8h is roasted at this temperature, then is cooled to room temperature.The heating rate is preferably 8-12 DEG C/min, more preferably
10℃/min。
In a preferred embodiment, the houghite precursor in step 1) can be used coprecipitation and be prepared, packet
Include following steps:
A) soluble zinc salt, soluble ferric iron salt are weighed first, and deionized water is added to be configured to mixed solution；
B) under continuous stirring, mixed solution made from step a) and sodium carbonate liquor are added dropwise in reactor；
Then suitable sodium hydroxide solution is added, the pH value in precipitation process is made to keep 9.5-10.5；
C) it is to be precipitated completely after, by sediment in mother liquor at 55-65 DEG C age overnight；
D) sediment is separated by filtration, washed several times with water, drying, obtains the houghite precursor.
Soluble zinc salt or molysite in step a) be selected from one of nitrate, sulfate, acetate, hydrochloride etc. or
It is a variety of, preferably nitrate；The molar ratio of Zn ion and iron ion be 2-4, preferably 3.
PH value in step b) is preferably 10.
Aging temperature in step c) is preferably 60 DEG C.
It, can also be according to specifically used in the process to catalyst shape and mechanical strength in the preparation method of the application catalyst
Requirement, and optional forming step 5 is introduced after the step 4)), common molding mode can be used, such as compression forming, squeeze
Molding, rotational forming etc. out can also introduce suitable common shaping assistant, such as Methyl cellulose as needed in forming process
The extrusion aid etc. of the lubricant of the adhesive of element etc, graphite, paraffin etc, sesbania powder etc.
Present inventor it has been investigated that, pass through the application institute by the way that the houghite precursor of active component will be impregnated
Specific drying mode-freeze-drying of selection, relative to other drying modes, such as drying is air-dried, microwave drying, helps to make
Active components distribution is more uniform in catalyst, improves the specific surface area of catalyst, and significantly reduces the roasting of catalyst
Temperature (such as active component precursors, when being bismuth nitrate, decomposition temperature is typically greater than 590 DEG C, and passes through freeze-drying, discovery
400 DEG C can be down to by maturing temperature is minimum, greatly reduce energy consumption), additionally aiding is allocated as each group in catalyst and carrier
It is firmly moderate, to improve the stability and service life of catalyst.
Through research, it has also been found that, the selected wet impregnation of the application (i.e. excess solution impregnation method) is impregnated relative to others
Technique, such as dry impregnation (i.e. isometric solution dipping method), multiple maceration, solvent evaporated method, inner hole deposition shallow lake method etc., more have
Help make Active components distribution in catalyst more uniform, and help to keep the active force of catalyst and carrier moderate, to mention
The high stability and service life of catalyst.In other words, the application is to specific selection made by impregnation technology, to final catalysis
Activity, stability and the service life of agent produce active influence.
Through research, it has also been found that, the application is by the control to roasting condition, especially temperature-gradient method and heating rate, relatively
It is warming up to calcination temperature in one-part form, or with other heating rates (i.e. heating rate is except the range of 5-15 DEG C/min) institute
The temperature-gradient method of progress can make ZnO and ZnFe in carrier2O4Exist with more suitable ratio, without will lead to ZnO or
ZnFe2O4Excessively, and similarly help to make each component active force in catalyst and carrier moderate, to improve catalyst
Stability and service life.
In terms of comprehensive, the application proposes the selection of impregnation technology, drying mode and roasting condition to catalyst performance
Height produces active influence.Although not knowing that factors above promotes upper occupied specific weight in final catalyst performance,
But if being unsatisfactory for any one in above-mentioned factor in preparation process, the activity and stability that will lead to catalyst occur bright
Aobvious decline.Thus present inventor is it is reasonable that factors above produces collaboration facilitation each other.
The application passes through reaction condition used in the production technology of synthesis of dimethyl carbonate via transesterification are as follows: reaction temperature is
55-100 DEG C, ethyl alcohol and ethylene carbonate (EC) molar ratio are 8-12, and catalyst amount is 1-5% (relative to ethylene carbonate
Weight).
The reaction temperature is preferably 55-80 DEG C, and the molar ratio of ethyl alcohol EC is preferably 8-10, and catalyst amount is preferably 2-
4.5% (relative to ethylene carbonate weight).
Present inventor it has been investigated that, although the catalyst of the application, in low temperature, such as 55 DEG C, catalyst amount is
When 4.5% (relative to ethylene carbonate weight), the yield of DMC is declined slightly, but due to reducing reaction temperature, is reduced and urged
The dosage of agent makes the economy of production technology be greatly improved on the whole.
Compared with prior art, the application has the beneficial effect that
1, in the application production technology used catalyst carrier component and active component Bi2O3And KOH, between this three
Synergistic effect beyond expectation is produced, makes catalyst that there is very high low-temperature catalytic activity.
2, catalyst long service life used in the application production technology, it is reusable multiple, it but still keeps good
Good activity and selectivity, catalyst performance is not in apparent decline, thus greatly improves the economy of production technology
Property.
3, pass through filtering after catalyst reaction used in the application production technology or centrifuge separation be i.e. recyclable,
Removal process is easy to operate, significantly reduces use cost.
4, catalyst preparation process used in the application production technology is simple, without roasting after houghite precursor is obtained
Burning can be used to load active component, not only reduce energy consumption, and facilitate carrier ZnO and ZnFe2O4It is deposited with suitable ratio
Additionally aiding keeps each component active force in catalyst and carrier moderate.
5, in the preparation process of catalyst used in the application production technology, to impregnation technology, drying mode and roasting
The selection of condition produces active influence to the raising of catalyst performance, and factors above produces collaboration each other and promotees
Into effect.
6, the production technology reaction time of the application is short, and reaction condition is mild, therefore significantly reduces carbonate synthesis two
The production cost of methyl esters.
Other advantage will be partly show in the following description, and can be partly able to by specific embodiment
Understand.Especially by point out in the dependent claims Chemical composition that, method and combinations thereof, will realize and obtain down
State advantage.It should be appreciated that general description and detailed description below above is merely exemplary and illustrative, rather than
It is restrictive.
Complementary definition
Material, compound, composition and component described herein, can be used for method and composition described herein,
Or it can be in connection or the production that can be used for implementing the method and prepare the composition or obtained as the method
Product.It should be appreciated that when disclosing combination, subset, interaction, the group etc. of these materials, although may not clearly have
Body refers to each and collective combinations and arrangement of these compounds, but specifically considers and describe wherein in this application
Each.For example, if open and a certain adjuvant component is discussed, and a variety of alternative actual forms of the component are discussed,
Then unless there is specific opposite instruction, each combination of possible adjuvant component and actual form is otherwise specifically considered
And arrangement.The concept is suitable for all aspects of the application, is including but not limited to making and using disclosed composition
Step in method.Therefore, if there is the multiple other steps that can be executed, then it should be appreciated that these other steps
Each can be executed by the combination of any specific embodiment or multiple embodiments of disclosed method, and
Each such combination is specifically considered, they should be considered as disclosing.
In claims in this specification and its later, refer to many terms, they should be defined as with
Lower meaning:
It must be noted that unless context is in addition clearly stipulate that otherwise such as institute in this specification and appended claims
Not only may include a referring to thing with, singular " one ", "/kind " and " should/described ", but may include multiple referring to thing (i.e.
Two or more, including two).Thus, for example, referring to that " pH adjusting agent " may include single pH adjusting agent or two
Kind or more mixture of pH adjusting agent, etc..
" optional " or " optionally " mean that the event then described or situation can occur or will not occur, and the description
Including the wherein event or the situation happened and the situation not occurred.For example, phrase " optional adjuvant component " is anticipated
Refer to that the adjuvant component may exist, can also be not present, and the description covers in composition comprising adjuvant component and group
Close two kinds of situations for not including adjuvant component in object.
Unless otherwise specified, therefore it and may include in the model about that the numberical range in the application, which is,
Enclose outer value.The numberical range can be expressed as in the application from " about " particular value and/or to " about " another particular value.
When stating such range comprising from one particular value and/or to another particular value.Similarly, when by making
When a certain particular value being expressed as approximation with antecedent " about ", it should be understood that its cover the particular value itself and by
In measurement or calculate caused technical field tolerance range.It is also understood that each in numberical range
Endpoint is important in the relationship with another endpoint and independently of another endpoint.
The parts by weight of element-specific or component in composition or product are referred in specification and last claims
Refer to the weight relationships stated in composition or product between the element or component and any other element or component with parts by weight.
Therefore, in the composition comprising 2 parts by weight of component X and 5 parts by weight of component Y, X and Y exist with the weight ratio of 2:5, and nothing
It whether include that other component exists with the ratio by composition.
Unless context in addition clearly stipulate that or have other meanings, or context or technical field based on context
The hint of interior ways customary, all scores and percentage otherwise referred in the application are by weight, and the weight of component
Total weight of the percentage based on the composition comprising the component or product.
"comprising", " comprising ", " having " and the similar terms referred in the application are not intended to exclude any optional group
Divide, the presence of step or program, regardless of whether specifically disclosing any optional component, step or program.It is doubted in order to avoid any
It asks, unless may include otherwise that one or more are additional by using all methods that term "comprising" requires there are state otherwise
Step, equipment part or component part and/or substance.In contrast, term " by ... form " exclude be not specifically delineated or
Any component, step or the program enumerated.Unless otherwise stated, otherwise term "or" refers to individually and in any combination
The member enumerated.
In addition, the side that the content of any referenced patent document or non-patent literature is all quoted in its entirety in the application
Formula is incorporated herein, especially with respect to disclosed in fields definition (any definition not provided specifically with the application not
Under unanimous circumstances) and common sense.
Specific embodiment
Iing is proposed the following example is to provide how to be made and evaluate the application institute to those skilled in the art
Entire disclosure and the description of compound state and claimed, composition, product, device and/or method,
And it is intended only to be illustrative, is not intended to be limiting the range that applicant is considered as its invention.Effort has been made to ensure
About the accuracy of digital (such as amount, temperature etc.), but it is contemplated that some errors and deviation.Unless otherwise specified, no
Then number is parts by weight, and temperature is DEG C to indicate or under environment temperature, and pressure is atmospheric pressure or close to atmospheric pressure.
There are reaction condition (such as concentration of component, required solvent, solvent mixture, temperature, pressure and other reaction ranges) and
It can be used for optimizing a variety of variations and combination of the condition of the product purity and yield that obtain by the method.It will only need
Reasonable routine experiment optimizes such method condition.
Embodiment 1:
With deionized water prepare 100mL zinc nitrate and ferric nitrate mixed solution A, wherein zinc ion with it is aluminum ions
Molar ratio is 2.Then the sodium carbonate liquor B of 100mL is prepared.Under continuous stirring, solution A and B are added dropwise to reactor
It is interior；Then the sodium hydroxide solution that suitable concentration is 2mol/L is added, the pH value in precipitation process is made to keep 9.5；It is to be precipitated
Completely after, by sediment in mother liquor at 55 DEG C age overnight；Sediment is separated by filtration, washed several times with water, at 100 DEG C do
Dry 12h obtains the houghite precursor.
The 6.5wt%, Bi of catalyst weight are accounted for by active component in final catalyst2O3: KOH (weight ratio)=1:2 matches
The maceration extract of bismuth nitrate and potassium hydroxide processed, wherein bismuth concentration is 0.2mol/L, and KOH concentration is 0.5mol/L.Then plus
Enter zinc-aluminum hydrotalcite precursor, carries out wet impregnation.Filter cake then is obtained by filtration, washes.Filter cake is freeze-dried, horse is then placed in
Not roasted under air atmosphere in furnace, first by desciccate with the heating rate of 8 DEG C/min by room temperature to 200 DEG C, keep the temperature 2h,
It then proceedes to be warming up to 400 DEG C with the heating rate of 8 DEG C/min, and roasts 8h at this temperature, be naturally cooling to after having roasted
Thus catalyst A is made in room temperature.
Embodiment 2
With deionized water prepare 100mL zinc nitrate and ferric nitrate mixed solution A, wherein zinc ion with it is aluminum ions
Molar ratio is 4.Then the sodium carbonate liquor B of 100mL is prepared.Under continuous stirring, solution A and B are added dropwise to reactor
It is interior；Then the sodium hydroxide solution that suitable concentration is 2mol/L is added, the pH value in precipitation process is made to keep 10.5；It is to be precipitated
Completely after, by sediment in mother liquor at 65 DEG C age overnight；Sediment is separated by filtration, washed several times with water, at 100 DEG C do
Dry 12h obtains the houghite precursor.
The 9.5wt%, Bi of catalyst weight are accounted for by active component in final catalyst2O3: KOH (weight ratio)=1:4 matches
The maceration extract of bismuth nitrate and potassium hydroxide processed, wherein bismuth concentration is 0.8mol/L, and KOH concentration is 1.8mol/L.Then plus
Enter zinc-aluminum hydrotalcite precursor, carries out wet impregnation.Filter cake then is obtained by filtration, washes.Filter cake is freeze-dried, horse is then placed in
Not roasted under air atmosphere in furnace, first by desciccate with the heating rate of 12 DEG C/min by room temperature to 250 DEG C, heat preservation
1h is then proceeded to be warming up to 550 DEG C with the heating rate of 12 DEG C/min, and is roasted 3h at this temperature, is dropped naturally after having roasted
It warms to room temperature, catalyst B is thus made.
Embodiment 3
With deionized water prepare 100mL zinc nitrate and ferric nitrate mixed solution A, wherein zinc ion with it is aluminum ions
Molar ratio is 3.Then the sodium carbonate liquor B of 100mL is prepared.Under continuous stirring, solution A and B are added dropwise to reactor
It is interior；Then the sodium hydroxide solution that suitable concentration is 2mol/L is added, the pH value in precipitation process is made to keep 10；It is to be precipitated complete
Quan Hou, by sediment in mother liquor at 60 DEG C age overnight；Sediment is separated by filtration, washed several times with water, the drying at 100 DEG C
12h obtains the houghite precursor.
The 7wt%, Bi of catalyst weight are accounted for by active component in final catalyst2O3: KOH (weight ratio)=1:3 is prepared
The maceration extract of bismuth nitrate and potassium hydroxide, wherein bismuth concentration is 0.5mol/L, and KOH concentration is 1.2mol/L.Then it is added
Zinc-aluminum hydrotalcite precursor carries out wet impregnation.Filter cake then is obtained by filtration, washes.Filter cake is freeze-dried, Muffle is then placed in
Roasted under air atmosphere in furnace, first by desciccate with the heating rate of 10 DEG C/min by room temperature to 220 DEG C, heat preservation
1.5h is then proceeded to be warming up to 450 DEG C with the heating rate of 10 DEG C/min, and is roasted 4h at this temperature, natural after having roasted
It is cooled to room temperature, catalyst C is thus made.
Comparative example 1
Preparation process is substantially the same manner as Example 3, and difference is only that: active component is only KOH.
Comparative example 2
Preparation process is substantially the same manner as Example 3, and difference is only that: active component is only Bi2O3。
Comparative example 3
Preparation process is substantially the same manner as Example 3, and difference is only that: be made houghite precursor after, with subsequent roasting
Under the identical roasting condition of burning condition, first by houghite precursor be fired into oxide carrier and then loaded on it is living
Property component.
Comparative example 4
Preparation process is substantially the same manner as Example 3, and difference is only that: by the filter cake after load active component using common
Drying mode (the dry 12h at 100 DEG C) is dried.
Comparative example 5
Preparation process is substantially the same manner as Example 3, and difference is only that: impregnation technology changes dry impregnation (isometric leaching into
Stain).
Comparative example 6
Preparation process is substantially the same manner as Example 3, and difference is only that: in roasting process directly by desciccate with 10 DEG C/
The heating rate of min is by room temperature to 450 DEG C (insulating process for eliminating interlude).
Catalytic performance test
The catalytic performance of catalyst obtained by embodiment 1-3, comparative example 1-6 is surveyed at reaction condition a respectively
Examination, test result is as shown in table 1, and wherein stability and service life are assessed based on number is reused, and reuses number
It is (active to decline with selectivity compared with initial activity and selectivity to refer to that the activity and selectivity of catalyst is basically unchanged
Amplitude less than the number that can be recycled in the case where 10%).
The catalyst is used to be catalyzed ethylene carbonate (EC) and ethyl alcohol ester and passes through ester exchange reaction carbonate synthesis diethyl
The reaction condition a of ester are as follows: reaction temperature is 60 DEG C, reaction time 4h, and the molar ratio of methanol and ethylene carbonate is 10, catalyst
Dosage be ethylene carbonate weight 5%；Product is analyzed by gas-chromatography thermal conductivity cell detector.
In addition, the catalyst of embodiment 3 has also been carried out performance test at reaction condition b: reaction temperature is 55 DEG C, instead
The molar ratio of 4h between seasonable, methanol and ethylene carbonate is 10, and the dosage of catalyst is the 4.5% of ethylene carbonate weight.
Table 1- catalyst performance test result
From the production technology that the test result of table 1 can be seen that the application, due to using the activity with specific composition
The catalyst that component and carrier are constituted, so that high DMC yield can be realized under mild reaction conditions, and due to being catalyzed
In agent preparation process, by load opportunity to active component, impregnation technology, drying mode and roasting condition specific selection with
Control, and keeps each component active force in catalyst and carrier moderate, so that catalyst be made to have good stability and longer
Service life, thus significantly reduce the production cost of the production technology of Synthesis of dimethyl carbonate, improve its economy.
In text of the statement, various publications are referred to.Disclosures of these publications full text is accordingly with reference side
During formula is incorporated herein, so that compound, composition and method described herein is described more fully with.
Various modifications and change can be made to compound described herein, composition and method.In view of specification and
The practice of compound, composition and method disclosed in the present application, compound described herein, composition and method it is other
Aspect will be evident.Specification and example are intended to be considered as illustrative.
Obviously, the above embodiments are merely examples for clarifying the description, and does not limit the embodiments.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or
It changes.There is no necessity and possibility to exhaust all the enbodiments.And it is extended from this it is obvious variation or
It changes still within the protection scope of the invention.
Claims (10)
1. a kind of production technology by synthesis of dimethyl carbonate via transesterification, which is characterized in that catalyst used is by 6-
The active component of 10wt% and the carrier composition of surplus, the active component is Bi2O3And KOH, Bi2O3: KOH (weight ratio)=
1:2-4；The carrier is zinc-iron metal composite oxide.
2. production technology according to claim 1, the carrier is roasted by houghite precursor and is made, general formula are as follows: [Zn2 + 1-xFe3+ x(OH)2]x+(CO3 2-)x/2·nH2O, wherein 0.2≤x≤0.33,1≤n≤10.
3. production technology according to claim 1 or 2, the content of the active component is preferably 6-8wt%, with catalyst
On the basis of total weight；X in the general formula is preferably 0.25≤x≤0.33.
4. production technology according to claim 1, wherein the preparation method of catalyst includes the following steps:
1) first, in accordance with the composition of final carrier, houghite precursor is made；
2) composition for pressing final catalyst, weighs KOH, soluble bismuth salt, deionized water is added to be configured to maceration extract；
3) in the maceration extract made from step 2), the obtained houghite precursor of step 1) is added, carries out wet impregnation；Then
Filter cake is filtered or be centrifugally separating to obtain, is washed；
4) filter cake is freeze-dried, then under air atmosphere, roasts 3-8h at 400-550 DEG C, be subsequently reduced to room temperature, can makes
Obtain catalyst prod.
5. production technology according to claim 4, co-precipitation legal system is can be used in the houghite precursor in the step 1)
It is standby to obtain, include the following steps:
A) soluble zinc salt, soluble ferric iron salt are weighed first, and deionized water is added to be configured to mixed solution；
B) under continuous stirring, mixed solution made from step a) and sodium carbonate liquor are added dropwise in reactor；Then
Suitable sodium hydroxide solution is added, the pH value in precipitation process is made to keep 9.5-10.5；
C) it is to be precipitated completely after, by sediment in mother liquor at 55-65 DEG C age overnight；
D) sediment is separated by filtration, washed several times with water, drying, obtains the houghite precursor.
6. production technology according to claim 4, bismuth concentration is 0.1-1mol/L in the maceration extract in step 2), more
Preferably 0.3-0.7mol/L；KOH concentration is 0.5-2mol/L, more preferably 1-1.5mol/L.
7. production technology according to claim 4, the roasting process of step 4) are as follows: by desciccate with 5-15 DEG C/min's
Heating rate, to 200-250 DEG C, is kept the temperature 1-2h, then proceedes to be warming up to the heating rate of 5-15 DEG C/min by room temperature
400-550 DEG C, and 3-8h is roasted at this temperature, then is cooled to room temperature.
8. production technology according to claim 4 can introduce optional forming step after step 4).
9. production technology according to claim 1, reaction condition therein are as follows: reaction temperature be 55-100 DEG C, ethyl alcohol with
Ethylene carbonate (EC) molar ratio is 8-12, and catalyst amount is 1-5% (relative to ethylene carbonate weight).
10. production technology according to claim 9, the reaction temperature is preferably 55-80 DEG C, and the molar ratio of ethyl alcohol EC is excellent
It is selected as 8-10, catalyst amount is preferably 2-4.5% (relative to ethylene carbonate weight).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910590296.XA CN110204444B (en) | 2019-07-02 | 2019-07-02 | Synthesis method of dimethyl carbonate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910590296.XA CN110204444B (en) | 2019-07-02 | 2019-07-02 | Synthesis method of dimethyl carbonate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110204444A true CN110204444A (en) | 2019-09-06 |
| CN110204444B CN110204444B (en) | 2022-04-22 |
Family
ID=67795798
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910590296.XA Active CN110204444B (en) | 2019-07-02 | 2019-07-02 | Synthesis method of dimethyl carbonate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110204444B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112156797A (en) * | 2020-09-10 | 2021-01-01 | 中国科学院山西煤炭化学研究所 | Catalyst for synthesizing dimethyl carbonate by ester exchange of cyclic carbonate and methanol, preparation method and application thereof |
| CN114210273A (en) * | 2021-12-24 | 2022-03-22 | 常州化工设计院有限公司 | Preparation process of ethylene carbonate |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105251496A (en) * | 2015-09-18 | 2016-01-20 | 四川泸天化股份有限公司 | Catalyst and method preparing dimethyl carbonate by using catalyst |
| CN106881074A (en) * | 2015-12-16 | 2017-06-23 | 陈锦章 | Solid base catalyst for producing biodiesel, method for producing same, and biodiesel production method using same |
| CN109603796A (en) * | 2018-12-14 | 2019-04-12 | 中海石油炼化有限责任公司 | A kind of solid base catalyst and its preparation method and application |
| CN109772286A (en) * | 2019-03-06 | 2019-05-21 | 中国海洋石油集团有限公司 | A kind of solid base catalyst and its preparation method and application |
| CN110128274A (en) * | 2019-05-28 | 2019-08-16 | 中国科学院成都有机化学有限公司 | A kind of method of dimethyl carbonate ester exchange synthesizing diphenyl carbonate |
| CN110252320A (en) * | 2019-07-02 | 2019-09-20 | 滕州京腾鑫汇新材料科技有限公司 | A kind of catalyst of Synthesis of dimethyl carbonate and preparation method thereof |
-
2019
- 2019-07-02 CN CN201910590296.XA patent/CN110204444B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105251496A (en) * | 2015-09-18 | 2016-01-20 | 四川泸天化股份有限公司 | Catalyst and method preparing dimethyl carbonate by using catalyst |
| CN106881074A (en) * | 2015-12-16 | 2017-06-23 | 陈锦章 | Solid base catalyst for producing biodiesel, method for producing same, and biodiesel production method using same |
| CN109603796A (en) * | 2018-12-14 | 2019-04-12 | 中海石油炼化有限责任公司 | A kind of solid base catalyst and its preparation method and application |
| CN109772286A (en) * | 2019-03-06 | 2019-05-21 | 中国海洋石油集团有限公司 | A kind of solid base catalyst and its preparation method and application |
| CN110128274A (en) * | 2019-05-28 | 2019-08-16 | 中国科学院成都有机化学有限公司 | A kind of method of dimethyl carbonate ester exchange synthesizing diphenyl carbonate |
| CN110252320A (en) * | 2019-07-02 | 2019-09-20 | 滕州京腾鑫汇新材料科技有限公司 | A kind of catalyst of Synthesis of dimethyl carbonate and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| 刘遂生: "《定性分析化学常识》", 31 March 1951, 中华书局股份有限公司 * |
| 杨德壬: "《无机化学（下）》", 30 April 1983, 上海科学技术出版社 * |
| 章定恒: ""水滑石前体法制备Fe掺杂ZnO纳米材料及其发光性能研究"", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112156797A (en) * | 2020-09-10 | 2021-01-01 | 中国科学院山西煤炭化学研究所 | Catalyst for synthesizing dimethyl carbonate by ester exchange of cyclic carbonate and methanol, preparation method and application thereof |
| CN112156797B (en) * | 2020-09-10 | 2022-02-15 | 中国科学院山西煤炭化学研究所 | Catalyst for synthesizing dimethyl carbonate by ester exchange of cyclic carbonate and methanol, preparation method and application thereof |
| CN114210273A (en) * | 2021-12-24 | 2022-03-22 | 常州化工设计院有限公司 | Preparation process of ethylene carbonate |
| CN114210273B (en) * | 2021-12-24 | 2023-09-05 | 常州化工设计院有限公司 | Preparation process of ethylene carbonate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110204444B (en) | 2022-04-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP3950123B1 (en) | Heterogeneous catalyst based on ionic liquid, and preparation method therefor and use thereof | |
| CN109772286B (en) | Solid base catalyst and preparation method and application thereof | |
| CN109821560B (en) | Catalyst for synthesizing dimethyl carbonate by ester exchange and application thereof | |
| CN110204444A (en) | Synthesis method of dimethyl carbonate | |
| CN1900047A (en) | Process for preparing methyl ethyl carbonate by ester exchanging reaction | |
| CN104001538B (en) | Ceria modified Ni SBA-15 catalyst and its preparation method and application | |
| CN108129314A (en) | By the method for ethylene carbonate, methanol and ethyl alcohol one-step synthesis methyl ethyl carbonate | |
| CN103801282A (en) | Solid base catalyst as well as preparation and application thereof | |
| CN110252320A (en) | A kind of catalyst of Synthesis of dimethyl carbonate and preparation method thereof | |
| CN108276279A (en) | The method of one-step synthesis carbonic acid asymmetry ester | |
| CN104907074B (en) | Ester through hydrogenation catalyst and preparation method thereof and the method for ester through hydrogenation reaction | |
| CN108047040A (en) | A kind of method of ethylene carbonate and alcohols one-step synthesis carbonic acid symmetrical ester | |
| CN108191661A (en) | By the method for ethylene oxide one-step synthesis methyl ethyl carbonate co-production ethylene glycol | |
| CN102259005B (en) | Catalyst for assisting coal natural gas methanation reactor and preparation method thereof | |
| CN105344355A (en) | Catalyst for preparing methane from coal-based synthetic gas, and preparation method thereof | |
| CN107308950A (en) | It is a kind of to prepare catalyst of mixed alcohol and its preparation method and application for synthesis gas | |
| CN101007766A (en) | Method for catalytic synthesis of diamyl carbonate and methyl amyl carbonate | |
| CN110787804A (en) | Hydrodeoxygenation sulfur-free nickel-based Ni/Al2O3-ZrO2Catalyst and process for preparing same | |
| CN102516027B (en) | Method for preparing catalyst for coproducing alcohol and ketone according to acetone hydrogenation method | |
| CN115301235A (en) | Catalyst for preparing high-carbon alcohol by hydrogenation of fatty acid methyl ester and preparation method and application thereof | |
| CN114736175A (en) | Method for preparing 5-hydroxymethylfurfural by catalyzing glucose in aqueous phase | |
| CN104353463B (en) | Anti-carbon synthesis gas methanation catalyst, preparation method and application thereof | |
| CN105296167B (en) | A kind of method of catalysis for preparing biodiesel oil | |
| CN112794859A (en) | Method for preparing LAC (cellulose/biomass) by catalyzing pyrolysis of cellulose/biomass by nickel-tin multi-element composite metal oxide | |
| CN106215939B (en) | The preparation method of biodiesel solid catalyst |
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 | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20220510 Address after: 063000 No. 905-1, 3rd floor, junxinli Central Plaza, Lubei District, Tangshan City, Hebei Province Patentee after: Tangshan good reputation Technology Development Co.,Ltd. Address before: 277500 Yikang North Road, Shannan Street, Tengzhou City, Zaozhuang City, Shandong Province (second floor of business building of Shandong Fuhui Metal Structure Engineering Co., Ltd.) Patentee before: Tengzhou Jingtengxinhui New Material Technology Co.,Ltd. |
|
| TR01 | Transfer of patent right |