CN110152694A - A kind of heterogeneous acetylene carbonylating catalyst and preparation method thereof, application - Google Patents
A kind of heterogeneous acetylene carbonylating catalyst and preparation method thereof, application Download PDFInfo
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Abstract
The present invention is a kind of heterogeneous acetylene carbonylating catalyst and preparation method thereof, application.A kind of heterogeneous acetylene carbonylating catalyst, comprising: major catalyst, co-catalyst, solvent and carrier；The major catalyst is nickel oxide-nickel oxide, is supported on the carrier；The co-catalyst is copper bromide；The carrier is expanded vermiculite；The solvent is tetrahydrofuran.The invention also discloses a kind of preparation methods of heterogeneous acetylene carbonylating catalyst, application.A kind of heterogeneous acetylene carbonylating catalyst of the present invention and preparation method thereof, application, which is heterogeneous catalysis, at low cost, can repeatedly recycle, and is reused, and has preferable anti-carbon performance, and yield and selectivity are high.
Description
Technical field
The invention belongs to catalyst technical fields, and in particular to a kind of heterogeneous acetylene carbonylating catalyst and its preparation side
Method, application.
Background technique
Acrylic acid is important monomer and basic chemical feedstock.It is widely used in production acrylate, polymer, plastics and
The consumer goods, and it is widely used in many fields of industry.In order to reduce dependence of the society to natural oil, from coal or gas product
The acrylic acid of middle synthesis high added value is an important prospect.The synthetic method will reduce acrylic acid synthesis and supply petroleum propylene
The dependence answered.Producing acrylic acid by the approach is the reaction based on water, CO and acetylene.It is that carboxylic is produced in acetylene chemistry
One of most important reaction of acid monomers, and take full advantage of the acetylene and CO product of calcium carbide.Acetylene for acrylic acid synthesizing
Carbonylation not only has important value in the reasonable use aspects of resource, but also also has value in terms of Green Chemistry.However,
The main problem that acrylic acid synthesizing is carbonylated by acetylene is catalyst efficiency.
1938, Reppe and its team developed the process route of acetylene carbonylation production acrylic acid, and are successfully realized
Industrialization, but due to Ni (CO)4Severe toxicity, after used by limitation, with homogeneous catalysis acrylic acid synthesizing carried out one again later
The research of series.
1963, Bhattacharyya team used the Metal Supporteds such as silica gel and Fe, Co, Ni SiO2As catalyst,
The reaction of carbonylation is had studied, the maximum yield of acrylic acid is 8%.Report the report of aluminum oxide nickel-loaded again later, but
Catalytic effect is unsatisfactory.
Later period in the 1970's, with the fast development of petrochemical industry, using propylene as the petroleum law of raw material gradually instead of with
Acetylene is the Reppe synthetic method of raw material.
Nineteen ninety-five closes the device in the last a set of acetylene method acrylic acid synthesizing in the world of Ludwig, Germany factory,
Petroleum law is directly instead of Reppe synthetic method, and the research of acetylene carbonylation acrylic acid synthesizing just stopped later, then it is few this
Aspect reports.
Zi Gong gas chemical industry research institute has studied nickel salt-copper salt catalyst from 1972-1990, and achieves certain
Achievement.Chengdu Institute of Organic Chemistry, Chinese Academy of Sciences first has studied nickel acetate-copper bromide-phosphorus-acid catalyst body so far in 1987
System has studied the catalyst system of palladium series and monophosphorous ligand modification again later, has obtained conversion of alkyne 75.8%, acrylic acid choosing
Select 98.6%.
So far synthesizing acrylic acid from acetylene carbonyl is studied by East China University of Science within 2007, they utilize nickel ion
The molecular sieve of exchange achieves certain achievement as catalyst, but molecular sieve is expensive, at high cost, undoubtedly increases second
The cost of alkynes carbonylation acrylic acid synthesizing.
In conclusion acetylene carbonylation generate the nearly all report catalyst of acrylic acid acetylene be all it is homogeneous, such as Ni
(OAc)2-CuBr2-CH3SO3H-PPh3, NiX2-CuX2(X=halogen) and Ni (CO)4Make catalyst separate and recycle it is extremely difficult,
And serious problems are also resulted in terms of environmental pollution.In addition, Non oil-based route method synthesis high added value acrylic acid and ester be
It is carried out under high temperature and pressure, height is required to equipment construction and technological operation, and acetylene is easy polymerization under high temperature and pressure and generates polymerization
Object or carbon distribution.But the using effect of heterogeneous carbonylation catalysts and bad, yield and selectivity be not high.
In view of this, developing a kind of yield and selective high, cheap heterogeneous acetylene carbonylating catalyst has weight
The research significance and industrial application value wanted.
Summary of the invention
The purpose of the present invention is to provide a kind of heterogeneous acetylene carbonylating catalyst, which is heterogeneous catalysis
Agent, it is at low cost, can repeatedly recycle, it reuses, and there is preferable anti-carbon performance, yield and selectivity are high.
To achieve the goals above, used technical solution are as follows:
A kind of heterogeneous acetylene carbonylating catalyst comprising: major catalyst, co-catalyst, solvent and carrier；
The major catalyst is nickel oxide, is supported on the carrier；
The co-catalyst is copper bromide；
The carrier is expanded vermiculite；
The solvent is tetrahydrofuran.
Further, the mass ratio of the gross mass and co-catalyst of the major catalyst and carrier is 1:0.05-0.2；
The mass volume ratio of the co-catalyst and solvent is 1:2-4g/L.
Further, the mass ratio of the gross mass and co-catalyst of the major catalyst and carrier is 1:0.1；
The mass volume ratio of the co-catalyst and solvent is 1:3g/L.
Further, in the gross mass of the major catalyst and carrier, the content of nickel is 3.37-24.94%.
Further, in the gross mass of the major catalyst and carrier, the content of nickel is 11.37%.
It is another object of the present invention to provide the preparation method of above-mentioned heterogeneous acetylene carbonylating catalyst, the preparations
Method is simple.
To achieve the goals above, used technical solution are as follows:
The preparation method of above-mentioned heterogeneous acetylene carbonylating catalyst, comprising the following steps:
(1) it after preparing expanded vermiculite, crushes, obtains carrier；
(2) it by carrier impregnation in nickel salt solution, after ultrasonic treatment, dry, pulverize, then calcine 3- at 500-600 DEG C
4h obtains the carrier of load major catalyst；
(3) carrier, co-catalyst and solvent that load major catalyst are mixed, obtains the heterogeneous acetylene carbonylation and urges
Agent.
Further, the nickel salt is nickel nitrate.
It is also an object of the present invention to provide the applications of above-mentioned heterogeneous acetylene carbonylating catalyst.
To achieve the goals above, used technical solution are as follows:
Application of the catalyst in acetylene carbonylation,
Above-mentioned heterogeneous acetylene carbonylating catalyst is added into reactor, then be passed through into reactor acetylene, CO and
Water, acetylene occur carbonylation and generate acrylic acid, and the acetylene pressure is 0.3MPa, and CO pressure is 3MPa, in reactor
Reaction temperature be 230-240 DEG C.
The utility model has the advantages that
1, before most of acrylic acid catalyze and synthesize is homogeneous catalyst so that product, catalyst are difficult to point
From, it is difficult to reuse, and carbonylating catalyst of the invention is a kind of heterogeneous catalysis, reduces separation costs, it can be more
Secondary recycling, and keep preferable catalytic effect.
2, carbonylating catalyst of the invention is using Ni as major catalyst, using mantoquita as co-catalyst, using vermiculite as carrier,
Using tetrahydrofuran as solvent, there is good anti-carbon performance, improve the selectivity of heterogeneous catalysis acrylic acid synthesizing, leads to
It crosses acetylene carbonylation and shows very big acrylic acid synthesis potentiality, there is important research significance and market value.
The carrier material vermiculite used is a kind of natural, cheap and easy to get carrier material, and the vermiculite after expansion has very
Good anti-carbon effect.
Using tetrahydrofuran as solvent, so that the reaction of CO and acetylene is carried out catalysis reaction in a liquid, reaction can be improved
Safety, meanwhile, the stability of reaction can be improved, by-product not easily generated avoids the decomposition of acetylene at high temperature under high pressure,
Play the role of anti-carbon.
Specific embodiment
In order to which the present invention is further explained, a kind of heterogeneous acetylene carbonylating catalyst and preparation method thereof, application, reach
It is expected that goal of the invention, in conjunction with the preferred embodiment, to a kind of heterogeneous acetylene carbonylating catalyst proposed according to the present invention
And preparation method thereof, application, specific embodiment, structure, feature and its effect, detailed description is as follows.In the following description,
What different " embodiment " or " embodiment " referred to is not necessarily the same embodiment.In addition, specific in one or more embodiments
Feature, structure or feature can be combined by any suitable form.
Elaborate a kind of heterogeneous acetylene carbonylating catalyst of the present invention and preparation method thereof, before, having must
The raw material and method etc. referred in the present invention is described further, to reach better effect.
Reagent of the present invention is commercially available.
The main component of vermiculite (VMT) is natural layered clay mineral, and main component is Al2O3, SiO2And MgO.It is one
Kind carrier material cheap and easy to get carries out acetylene carbonylation using the catalyst prepared by nickel load vermiculite, achieves very
Good conversion ratio and yield.
Vermiculite in the embodiment of the present invention is using Xinlong vermiculite Co., Ltd in Sinkiang jade, China.
After having understood above-mentioned raw materials and method etc., below in conjunction with specific embodiment to a kind of heterogeneous second of the present invention
Alkynes carbonylating catalyst and preparation method thereof, using being further described in detail:
The technical solution of the present invention is as follows:
(1) it after preparing expanded vermiculite, crushes, obtains carrier；
(2) it by carrier impregnation in the nickel salt solution of various concentration, after ultrasonic treatment, dry, pulverize, then in 500-600
3-4h is calcined at DEG C, obtains the carrier of load major catalyst (nickel oxide)；
(3) carrier, co-catalyst (copper bromide) and solvent (tetrahydrofuran) that will load major catalyst mix, and obtain described
Heterogeneous acetylene carbonylating catalyst.
Preferably, the mass ratio of the gross mass and co-catalyst of the major catalyst and carrier is 1:0.05-0.2；
The mass volume ratio of the co-catalyst and solvent is 1:2-4g/L.
It is further preferred that the gross mass of the major catalyst and carrier and the mass ratio of co-catalyst are 1:0.1；
The mass volume ratio of the co-catalyst and solvent is 1:3g/L.
Preferably, in the gross mass of the major catalyst and carrier, the content of nickel is 3.37-24.94%.
It is further preferred that the content of nickel is 11.37% in the gross mass of the major catalyst and carrier.
Preferably, the nickel salt is nickel nitrate.
Embodiment 1.
Specific steps are as follows:
(1) it prepares expanded vermiculite (vermiculite abbreviation VMT): VMT (15g) and H being added into 500mL beaker2O2(30% concentration,
150mL).Beaker is immersed in 85 DEG C of water bath with thermostatic control 4 hours, to realize thermostatic expansion, and by gained mixture at 720W
Microwave heating 4min.Then mixture is placed in 115 DEG C of baking oven 11 hours.Obtained expansion multilayer VMT is ground, and is led to
Screening is sieved with 100 mesh sieve, carrier is obtained.Then using preposition in closed glass drying receptacle.
(2) catalyst the preparation of NiO/VMT catalyst: is converted for the VMT of acquisition by wet impregnation.Use various concentration
Ni (NO3)2·6H2O solution impregnating carrier obtains the catalyst precarsor of different Ni mass percents.
After precursor is ultrasonically treated 30 minutes, and dried 11 hours at a constant temperature at 115 DEG C.Then by the drying of acquisition
Product crushes in the agate mortar.Then, it is calcined 3-4 hours at 500-600 DEG C using Muffle furnace, obtains load major catalyst
Carrier, i.e. NiO/VMT catalyst.
(3) in an experiment, the NiO/VMT catalyst prepared by 1g, 30mL H2O, 200-400mL tetrahydrofuran (THF) and
0.05-0.2g co-catalyst (copper bromide) sequentially adds in reactor.After sealing reactor, N is used2Sky in purge
Gas.Then, the acetylene gas of 0.3MPa and the CO gas (being controlled by mass flowmenter) of 3MPa are successively introduced.
Then start constant agitator (500rpm), carrier gas reactor (i.e. 500mL reaction kettle) is quickly heated up into 230-
240 DEG C, and keep temperature constant until pressure no longer reduces, showing to react terminates.Opening cools down water unit and will immediately after
Reactor is rapidly cooled to room temperature.Residual gas after reaction is collected into gas collection bag by mass flowmenter.Use gas
The gas and liquid of analysis of hplc reaction.Catalyst is recycled and is tested, liquid and washing catalyst after filtering reaction.
Then the catalyst of acquisition is dry at 120 DEG C in vacuum drying oven, and it is applied to subsequent operation.
Embodiment 2.
Operating procedure is same as Example 1.Difference are as follows:
(2) calcination temperature is 550 DEG C, time 3.5h, and the load capacity of nickel is 11.37% in NiO/VMT catalyst.
(3) additional amount of NiO/VMT catalyst is 1g, and the additional amount of tetrahydrofuran is 300mL.Start constant agitator,
Carrier gas reactor is quickly heated up to 235 DEG C, reaction time 60min.
The yield of the conversion ratio of acetylene, the selectivity of acrylic acid and acetylene is shown in Table 1.
Embodiment 3.
Operating procedure is same as Example 2.Difference are as follows:
(2) load capacity of nickel is 0% in NiO/VMT catalyst.
The yield of the conversion ratio of acetylene, the selectivity of acrylic acid and acetylene is shown in Table 1.
Embodiment 4.
Operating procedure is same as Example 2.Difference are as follows:
(2) load capacity of nickel is 1.04% in NiO/VMT catalyst.
The yield of the conversion ratio of acetylene, the selectivity of acrylic acid and acetylene is shown in Table 1.
Embodiment 5.
Operating procedure is same as Example 2.Difference are as follows:
(2) load capacity of nickel is 3.37% in NiO/VMT catalyst.
The yield of the conversion ratio of acetylene, the selectivity of acrylic acid and acetylene is shown in Table 1.
Embodiment 6.
Operating procedure is same as Example 2.Difference are as follows:
(2) load capacity of nickel is 6.13% in NiO/VMT catalyst.
The yield of the conversion ratio of acetylene, the selectivity of acrylic acid and acetylene is shown in Table 1.
Embodiment 7.
Operating procedure is same as Example 2.Difference are as follows:
(2) load capacity of nickel is 9.43% in NiO/VMT catalyst.
The yield of the conversion ratio of acetylene, the selectivity of acrylic acid and acetylene is shown in Table 1.
Embodiment 8.
Operating procedure is same as Example 2.Difference are as follows:
(2) load capacity of nickel is 13.46% in NiO/VMT catalyst.
The yield of the conversion ratio of acetylene, the selectivity of acrylic acid and acetylene is shown in Table 1.
Embodiment 9.
Operating procedure is same as Example 2.Difference are as follows:
(2) load capacity of nickel is 18.49% in NiO/VMT catalyst.
The yield of the conversion ratio of acetylene, the selectivity of acrylic acid and acetylene is shown in Table 1.
Embodiment 10.
Operating procedure is same as Example 2.Difference are as follows:
(2) load capacity of nickel is 24.94% in NiO/VMT catalyst.
The yield of the conversion ratio of acetylene, the selectivity of acrylic acid and acetylene is shown in Table 1.
The screening of the different nickel loadings of table 1,
As shown in Table 1, for load capacity in 3.37-24.94%, selectivity and yield are preferable.Wherein, when nickel loading exists
When 11.37%, selectivity and yield are best.
Embodiment 11.
Operating procedure is same as Example 2.Difference are as follows:
(3) additional amount of copper bromide is 0g.
The yield of the conversion ratio of acetylene, the selectivity of acrylic acid and acetylene is shown in Table 2.
Embodiment 12.
Operating procedure is same as Example 2.Difference are as follows:
(3) additional amount of copper bromide is 0.03g.
The yield of the conversion ratio of acetylene, the selectivity of acrylic acid and acetylene is shown in Table 2.
Embodiment 13.
Operating procedure is same as Example 2.Difference are as follows:
(3) additional amount of copper bromide is 0.05g.
The yield of the conversion ratio of acetylene, the selectivity of acrylic acid and acetylene is shown in Table 2.
Embodiment 14.
Operating procedure is same as Example 2.Difference are as follows:
(3) additional amount of copper bromide is 0.2g.
The yield of the conversion ratio of acetylene, the selectivity of acrylic acid and acetylene is shown in Table 2.
Embodiment 15.
Operating procedure is same as Example 2.Difference are as follows:
(3) additional amount of copper bromide is 0.3g.
The yield of the conversion ratio of acetylene, the selectivity of acrylic acid and acetylene is shown in Table 2.
Embodiment 16.
Operating procedure is same as Example 2.Difference are as follows:
(3) additional amount of copper bromide is 0.4g.
The yield of the conversion ratio of acetylene, the selectivity of acrylic acid and acetylene is shown in Table 2.
The screening of different bromination amount of copper is added in table 2,
| Catalyst | The amount (g) of copper bromide | Conversion ratio (%) | Selectivity (%) | Yield (%) |
| Embodiment 11 | 0 | 18.57 | 3.45 | 0.64 |
| Embodiment 12 | 0.03 | 56.94 | 63.59 | 36.21 |
| Embodiment 13 | 0.05 | 73.77 | 84.18 | 62.1 |
| Embodiment 2 | 0.1 | 89.51 | 92.88 | 83.14 |
| Embodiment 14 | 0.2 | 89.95 | 84.86 | 76.33 |
| Embodiment 15 | 0.3 | 90.52 | 72.6 | 65.72 |
| Embodiment 16 | 0.4 | 91.08 | 66.19 | 60.29 |
As shown in Table 2, with the increase of copper bromide dosage, conversion ratio is increasing always.But the dosage of copper bromide is from 0
To 0.1g, selectivity and yield rise always, but the dosage of copper bromide is further added by, selectivity and yield decline.
Embodiment 17.
Operating procedure is same as Example 2.Difference are as follows:
(3) additional amount of tetrahydrofuran is 200mL.
The yield of the conversion ratio of acetylene, the selectivity of acrylic acid and acetylene is shown in Table 3.
Embodiment 18.
Operating procedure is same as Example 2.Difference are as follows:
(3) additional amount of tetrahydrofuran is 250mL.
The yield of the conversion ratio of acetylene, the selectivity of acrylic acid and acetylene is shown in Table 3.
Embodiment 19.
Operating procedure is same as Example 2.Difference are as follows:
(3) additional amount of tetrahydrofuran is 350mL.
The yield of the conversion ratio of acetylene, the selectivity of acrylic acid and acetylene is shown in Table 3.
Embodiment 20.
Operating procedure is same as Example 2.Difference are as follows:
(3) additional amount of tetrahydrofuran is 400mL.
The yield of the conversion ratio of acetylene, the selectivity of acrylic acid and acetylene is shown in Table 3.
The screening of tetrahydrofuran amount, (carrying out in the reaction kettle of 500ml) is added in table 3.
| Catalyst | Tetrahydrofuran amount (mL) | Conversion ratio (%) | Selectivity (%) | Yield (%) |
| Embodiment 17 | 200 | 91.64 | 87.35 | 80.05 |
| Embodiment 18 | 250 | 90.29 | 90.37 | 81.61 |
| Embodiment 2 | 300 | 89.51 | 92.88 | 83.14 |
| Embodiment 19 | 350 | 89.44 | 92.68 | 82.89 |
| Embodiment 20 | 400 | 89.09 | 92.34 | 82.27 |
As shown in Table 3, when the dosage of tetrahydrofuran is 200-400mL, selectivity and yield are all relatively good.
1, thermogravimetric analysis
Using conventional method in that art, carry out active constituent load capacity under the same conditions, nickel load different carriers
The thermogravimetric analysis of catalyst, the results are shown in Table 4.
Table 4
| The catalyst of nickel load different carriers | The carbon distribution (%) generated in reaction process |
| Embodiment 2 (nickel load vermiculite) | 3.03 |
| Nickel load NaY molecular sieve | 7.62 |
| Nickel load HY molecular sieve | 16.46 |
| Nickel load MCM-41 molecular sieve | 8.4 |
| Nickel load talcum powder | 23.35 |
Table 4 shows the thermogravimetric characterization result of post catalyst reaction.Nickel load vermiculite, nickel are determined using thermogravimetry
NaY molecular sieve is loaded, nickel load HY molecular sieve, nickel load MCM-41 molecular sieve and nickel load talcum powder catalyst are in the air stream
Carbon distribution loss, the results are shown in Table 4, and the carbon deposit that nickel load vermiculite catalyst is formed during the reaction is minimum, and carbon deposition quantity is
3.03%, nickel load NaY molecular sieve, nickel load HY molecular sieve, the carbon distribution of nickel load MCM-41 molecular sieve and nickel load talcum powder
Amount is 7.62%.16.46%, 8.4% and 23.35%.The result shows that nickel load vermiculite catalyst has good anti-carbon
Can, it is that a kind of selectivity is good, the good catalyst of stability.
2, the recycling experiment of different catalysts
Using conventional method in that art, carry out active constituent load capacity under the same conditions, nickel load different carriers
The recycling of catalyst is tested, and the results are shown in Table 5.
Table 5
As shown in Table 5, nickel load MCM-41 molecular sieve catalyst is after circulation 3 times, and basic yield is 0, catalyst ineffective.
Nickel load NaY molecular sieve and the using effect of nickel load talcum powder catalyst are with the increase of cycle-index, and using effect is substantially
Degree decline.And catalyst of the invention, after being reused many times, although effect has decline, but fall is minimum.As a result table
It is bright, catalyst inactivation of the invention it is relatively slow, and can be recycled for multiple times.
The above is only the preferred embodiment of the embodiment of the present invention, not makees any shape to the embodiment of the present invention
Limitation in formula, any simple modification to the above embodiments of technical spirit according to an embodiment of the present invention, equivalent variations
With modification, in the range of still falling within technical solution of the embodiment of the present invention.
Claims (8)
1. a kind of heterogeneous acetylene carbonylating catalyst, characterized in that it comprises: major catalyst, co-catalyst, solvent and load
Body；
The major catalyst is nickel oxide, is supported on the carrier；
The co-catalyst is copper bromide；
The carrier is expanded vermiculite；
The solvent is tetrahydrofuran.
2. heterogeneous acetylene carbonylating catalyst according to claim 1, which is characterized in that
The gross mass of the major catalyst and carrier and the mass ratio of co-catalyst are 1:0.05-0.2；
The mass volume ratio of the co-catalyst and solvent is 1:2-4g/L.
3. heterogeneous acetylene carbonylating catalyst according to claim 2, which is characterized in that
The gross mass of the major catalyst and carrier and the mass ratio of co-catalyst are 1:0.1；
The mass volume ratio of the co-catalyst and solvent is 1:3g/L.
4. heterogeneous acetylene carbonylating catalyst according to claim 1, which is characterized in that
In the gross mass of the major catalyst and carrier, the content of nickel is 3.37-24.94%.
5. heterogeneous acetylene carbonylating catalyst according to claim 4, which is characterized in that
In the gross mass of the major catalyst and carrier, the content of nickel is 11.37%.
6. the preparation method of the described in any item heterogeneous acetylene carbonylating catalysts of claim 1-5, which is characterized in that including
Following steps:
(1) it after preparing expanded vermiculite, crushes, obtains carrier；
(2) it by carrier impregnation in nickel salt solution, after ultrasonic treatment, dry, pulverize, then calcine 3-4h at 500-600 DEG C, obtain
To the carrier of load major catalyst；
(3) carrier, co-catalyst and solvent that load major catalyst are mixed, obtains the heterogeneous acetylene carbonylation catalyst
Agent.
7. preparation method according to claim 6, which is characterized in that
The nickel salt is nickel nitrate.
8. application of the catalyst in acetylene carbonylation, it is characterised in that:
The described in any item heterogeneous acetylene carbonylating catalysts of claim 1-5 are added into reactor, then into reactor
It is passed through acetylene, CO and water, acetylene occurs carbonylation and generates acrylic acid, and the acetylene pressure is 0.3MPa, and CO pressure is
3MPa, the reaction temperature in reactor are 230-240 DEG C.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1303873A (en) * | 1999-12-27 | 2001-07-18 | 住友化学工业株式会社 | Catalyst for additive polymerization reaction and process for preparing additive polymer using same |
| CN101768070A (en) * | 2009-01-06 | 2010-07-07 | 中国科学院成都有机化学有限公司 | Method for synthesizing crylic acid by catalyzing acetylene carbonyl through palladium |
| CN107118093A (en) * | 2017-05-09 | 2017-09-01 | 北京华福工程有限公司 | Prepare acrylic acid |
| CN107185584A (en) * | 2017-05-05 | 2017-09-22 | 北京华福工程有限公司 | Catalyst for acetylene acrylic acid synthesizing ester of low-carbon alcohol and its production and use |
| CN107602369A (en) * | 2017-02-28 | 2018-01-19 | 新疆中泰化学股份有限公司 | A kind of preparation method of acrylic acid or acrylate |
-
2019
- 2019-06-21 CN CN201910539762.1A patent/CN110152694B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1303873A (en) * | 1999-12-27 | 2001-07-18 | 住友化学工业株式会社 | Catalyst for additive polymerization reaction and process for preparing additive polymer using same |
| CN101768070A (en) * | 2009-01-06 | 2010-07-07 | 中国科学院成都有机化学有限公司 | Method for synthesizing crylic acid by catalyzing acetylene carbonyl through palladium |
| CN107602369A (en) * | 2017-02-28 | 2018-01-19 | 新疆中泰化学股份有限公司 | A kind of preparation method of acrylic acid or acrylate |
| CN107185584A (en) * | 2017-05-05 | 2017-09-22 | 北京华福工程有限公司 | Catalyst for acetylene acrylic acid synthesizing ester of low-carbon alcohol and its production and use |
| CN107118093A (en) * | 2017-05-09 | 2017-09-01 | 北京华福工程有限公司 | Prepare acrylic acid |
Non-Patent Citations (3)
| Title |
|---|
| HONG SUB CHOI ET AL.: ""Nickel oxide-silica core-shell catalyst for acetylene hydroxycarbonylation"", 《CATALYSIS COMMUNICATIONS》 * |
| PANPAN LI ET AL.: ""High efficient nickel/vermiculite catalyst prepared via microwave irradiation-assisted synthesis for carbon monoxide methanation"", 《FUEL》 * |
| 安一哲等: ""高压法乙炔碳基化合成丙烯酸"", 《天然气化工》 * |
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