CN107118093A - Prepare acrylic acid - Google Patents
Prepare acrylic acid Download PDFInfo
- Publication number
- CN107118093A CN107118093A CN201710322606.0A CN201710322606A CN107118093A CN 107118093 A CN107118093 A CN 107118093A CN 201710322606 A CN201710322606 A CN 201710322606A CN 107118093 A CN107118093 A CN 107118093A
- Authority
- CN
- China
- Prior art keywords
- acrylic acid
- molecular sieve
- catalyst
- acetylene
- prepared according
- 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
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- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims abstract description 65
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000003054 catalyst Substances 0.000 claims abstract description 36
- 239000002808 molecular sieve Substances 0.000 claims abstract description 36
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims abstract description 34
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 21
- 239000010949 copper Substances 0.000 claims abstract description 21
- 150000002816 nickel compounds Chemical class 0.000 claims abstract description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052802 copper Inorganic materials 0.000 claims abstract description 16
- 239000003960 organic solvent Substances 0.000 claims abstract description 16
- -1 copper halide Chemical class 0.000 claims abstract description 10
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 claims abstract description 9
- 230000026030 halogenation Effects 0.000 claims abstract description 8
- 238000005658 halogenation reaction Methods 0.000 claims abstract description 8
- 229910001453 nickel ion Inorganic materials 0.000 claims abstract description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 3
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical class CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 17
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 239000007789 gas Substances 0.000 description 10
- 125000001967 indiganyl group Chemical group [H][In]([H])[*] 0.000 description 5
- 229920006395 saturated elastomer Polymers 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- 229910021590 Copper(II) bromide Inorganic materials 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(II) bromide Substances [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000006315 carbonylation Effects 0.000 description 2
- 238000005810 carbonylation reaction Methods 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000005997 Calcium carbide Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- GNMQOUGYKPVJRR-UHFFFAOYSA-N nickel(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Ni+3].[Ni+3] GNMQOUGYKPVJRR-UHFFFAOYSA-N 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical class [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical class [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- CLZWAWBPWVRRGI-UHFFFAOYSA-N tert-butyl 2-[2-[2-[2-[bis[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]amino]-5-bromophenoxy]ethoxy]-4-methyl-n-[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]anilino]acetate Chemical compound CC1=CC=C(N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)C(OCCOC=2C(=CC=C(Br)C=2)N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)=C1 CLZWAWBPWVRRGI-UHFFFAOYSA-N 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/10—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide
- C07C51/14—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide on a carbon-to-carbon unsaturated bond in organic compounds
-
- 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
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
- B01J29/14—Iron group metals or copper
- B01J29/146—Y-type faujasite
-
- 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
- B01J29/72—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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO compounds]
-
- 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
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses preparing acrylic acid, including：Catalyst is mixed with organic solvent and water in autoclave；Acetylene and carbon monoxide are passed through into the autoclave, and acetylene, carbon monoxide and water described in the catalyst is reacted, to obtain acrylic acid, wherein, the catalyst is made up of nickel compound containing, copper halide and molecular sieve, nickel ion and Cu in the copper halide in the nickel compound containing2+Mol ratio be (2~5):1, the quality of the molecular sieve is the nickel compound containing and the 0.1~20% of the halogenation copper mass summation.This method by using production cost it is low, stability, catalytic activity and the high catalyst acetylene of selectivity generate acrylic acid with carbon monoxide and water reaction, prepare acrylic acid so as to low cost and high yield, have broad application prospects.
Description
Technical field
The present invention relates to chemical technology field, specifically, the present invention relates to prepare acrylic acid.
Background technology
Contain a carbon-to-carbon double bond and a carboxyl in acrylic molecules, be a kind of important Elementary Chemical Industry raw material, extensively
Applied to fields such as coating, weaving, adhesive, leather, fibers.
Synthesis of conjugated carboxylic alkeneacid mainly has three kinds, i.e. acrylonitrile hydrolysis method, propylene fraction oxidizing process and acetylene carbonyl to close
Cheng Fa, acrylonitrile hydrolysis method is eliminated already due to severe toxicity.At present, the industrial production of acrylic acid is mainly aoxidized using propylene fraction
Method and acetylene oxo synthesis.Propylene fraction oxidizing process is using cheap propylene as raw material, and production cost is relatively low, but this method is undue
Rely on very nervous petroleum resources.And Carbonylation of Acetylene method is independent of oil, be particularly suitable for oil-poor, rich gas, rich coal country or
Regional development fine chemistry industry.China's coal, natural gas resource enrich, and contain in rich electricity production stone, and calcium carbide legal system acetylene tail gas
Have substantial amounts of carbon monoxide can as synthesizing acrylic acid from acetylene carbonyl carbonyl source, therefore, the method China development have money
Source advantage.
Synthesizing acrylic acid from acetylene carbonyl finds that the catalyst used at that time is Ni for German scholar Reppe earliest
(CO)4, greatly, labor safety is difficult to ensure that this catalyst toxicity.Then, BASF AG improves it and is applied to industrial production.
Although the catalyst after improvement is with good catalytic activity, serious to equipment corrosion, carbon distribution is particularly prone to, pipe is blocked
Road.
Therefore, the existing acrylic acid for preparing still has much room for improvement.
The content of the invention
It is contemplated that at least solving one of technical problem in correlation technique to a certain extent.Therefore, the present invention
One purpose is that proposition prepares acrylic acid.This method by using production cost it is low, stability, catalytic activity and
The high catalyst acetylene of selectivity and carbon monoxide and water reaction generation acrylic acid, so as to the system of low cost and high yield
It is standby to obtain acrylic acid, have broad application prospects.
In one aspect of the invention, the present invention proposes one kind and prepares acrylic acid.According to the implementation of the present invention
Example, this method includes：Catalyst is mixed with organic solvent and water in autoclave；Acetylene is passed through into the autoclave
And carbon monoxide, and acetylene, carbon monoxide and water described in the catalyst is reacted, to obtain acrylic acid, its
In, the catalyst is made up of nickel compound containing, copper halide and molecular sieve, nickel ion and the halogenation in the nickel compound containing
Cu in copper2+Mol ratio be (2~5):1, the quality of the molecular sieve is that the nickel compound containing and the halogenation copper mass are total
The 0.1~20% of sum.
Embodiments in accordance with the present invention, this method by using production cost it is low, stability, catalytic activity and selectivity
High catalyst acetylene and carbon monoxide and water reaction generation acrylic acid, so as to preparing for low cost and high yield
Acrylic acid, has broad application prospects.
In addition, the acrylic acid according to the above embodiment of the present invention for preparing can also have technology additional as follows special
Levy：
In some embodiments of the invention, the nickel compound containing is halide, sulfate, acetate, the nitric acid of nickel
One kind in salt, hydroxide and oxide.Thus, it is possible to further improve the catalytic activity and selectivity of the catalyst.
In some embodiments of the invention, the molecular sieve include selected from beta-molecular sieve, A type molecular sieve, X-type molecular sieve,
At least one of Y type molecular sieve, ZSM-5, ZSM-22, SAPO-34 and SAPO-11.Thus, it is possible to be urged described in further improving
Stability, catalytic activity and the selectivity of agent.
In some embodiments of the invention, the organic solvent includes being selected from tetrahydrofuran (THF), 2- methyl tetrahydrochysene furans
Mutter, at least one of acetone, 1-METHYLPYRROLIDONE, N,N-dimethylformamide.Thus, it is possible to further improve acrylic acid
Yield.
In some embodiments of the invention, the quality of the water is the 10~25% of the organic solvent quality.Thus,
The yield of acrylic acid can further be improved.
In some embodiments of the invention, the quality of the catalyst is the organic solvent and the water gross mass
0.1~10%.Thus, it is possible to further improve the yield of acrylic acid.
In some embodiments of the invention, the mol ratio of the acetylene and the carbon monoxide is 1:(1~15).By
This, can further improve the yield of acrylic acid.
In some embodiments of the invention, the reaction is completed at a temperature of 170~230 degrees Celsius.Thus,
The yield of acrylic acid can further be improved.
In some embodiments of the invention, the reaction is completed under 5~11MPa pressure.Thus, it is possible to enter
One step improves the yield of acrylic acid.
In some embodiments of the invention, the reaction is that 25~120min of carry out is completed.Thus, it is possible to further
Improve the yield of acrylic acid.
The additional aspect and advantage of the present invention will be set forth in part in the description, and will partly become from the following description
Obtain substantially, or recognized by the practice of the present invention.
Brief description of the drawings
The above-mentioned and/or additional aspect and advantage of the present invention will become from description of the accompanying drawings below to embodiment is combined
Substantially and be readily appreciated that, wherein：
Fig. 1 is according to an embodiment of the invention to prepare acrylic acid schematic flow sheet.
Embodiment
Embodiments of the invention are described below in detail.The embodiments described below is exemplary, is only used for explaining this hair
It is bright, and be not considered as limiting the invention.Unreceipted particular technique or condition in embodiment, according to text in the art
Offer described technology or condition or carried out according to product description.Agents useful for same or the unreceipted production firm person of instrument,
For can be by the conventional products of acquisition purchased in market.
In one aspect of the invention, the present invention proposes one kind and prepares acrylic acid.According to the implementation of the present invention
Example, this method includes：Catalyst is mixed with organic solvent and water in autoclave；Acetylene is passed through into the autoclave
And carbon monoxide, and acetylene, carbon monoxide and water described in the catalyst is reacted, to obtain acrylic acid, its
In, the catalyst is made up of nickel compound containing, copper halide and molecular sieve, nickel ion and the halogenation in the nickel compound containing
Cu in copper2+Mol ratio be (2~5):1, the quality of the molecular sieve is that the nickel compound containing and the halogenation copper mass are total
The 0.1~20% of sum.
The acrylic acid for preparing according to embodiments of the present invention is described in detail below with reference to Fig. 1.According to this hair
Bright embodiment, this method includes：
S100：Catalyst is mixed with solvent and water
In the step, catalyst is mixed with organic solvent and water in autoclave, wherein, catalyst has nickeliferousization
Nickel ion and Cu in copper halide in compound, copper halide and molecular sieve composition, nickel compound containing2+Mol ratio be (2~5):1, point
The quality of son sieve is nickel compound containing and the 0.1~20% of halogenation copper mass summation.Inventor has found that copper halide has activation second
The effect of alkynes, can improve the conversion ratio of acetylene, nickel ion as active component, it is necessary to keep certain concentration, therefore nickel from
Sub- content is higher than Cu2+Content, now the selectivity to acrylic acid is higher.It is more that the addition of molecular sieve enables catalyst system and catalyzing to adsorb
Acetylene and CO, it is possible to increase reaction rate, but when molecular sieve addition is excessive, easily trigger the polymerization of acetylene and reduce
The selectivity of target product acrylic acid.
Embodiments in accordance with the present invention, the species of nickel compound containing is not particularly restricted, and those skilled in the art can be with
Selected according to actual needs, according to a particular embodiment of the invention, nickel compound containing can be halide, the sulfuric acid of nickel
One kind in salt, acetate, nitrate, hydroxide and oxide.Thus, it is possible to which the catalysis for further improving catalyst is lived
Property.
Embodiments in accordance with the present invention, the species of molecular sieve is not particularly restricted, and those skilled in the art can basis
It is actually needed and is selected, molecular sieve can includes being selected from beta-molecular sieve, A type molecular sieve, X-type molecular sieve, Y type molecular sieve, ZSM-
5th, at least one of ZSM-22, SAPO-34 and SAPO-11.Inventor has found that molecular sieve has larger specific surface area, inhales
Attached ability is strong, and with certain acidity, by using molecular sieve as catalytic component, can increase acetylene and CO absorption
Amount, makes to contact more fully between reactant, improves reaction rate.
Embodiments in accordance with the present invention, the species of organic solvent is not particularly restricted, and those skilled in the art can root
Selected according to being actually needed, according to a particular embodiment of the invention, organic solvent can include being selected from tetrahydrofuran, 2- methyl
At least one of tetrahydrofuran, acetone, 1-METHYLPYRROLIDONE, N,N-dimethylformamide.Inventor passes through many experiments
It was unexpectedly observed that above-mentioned organic solvent is big to the solubility of acetylene, it is possible thereby to ensure at low pressures, have in liquid phase compared with
High concentration of acetylene, so that being easy to acetylene occurs carbonylation, while can avoid handling acetylene under elevated pressure conditions again
It is dangerous.
Embodiments in accordance with the present invention, the addition of water is not particularly restricted, and those skilled in the art can be according to reality
Border needs to be selected, according to a particular embodiment of the invention, and the addition (quality) of water can be the 10 of organic solvent quality
~25%.Inventor is by many experiments it was unexpectedly observed that only when water and organic solvent are maintained under conditions of said ratio
Just be conducive to the dissolving of catalyst and acetylene, so as to further improve the yield that reaction obtains acrylic acid.If the amount of water is excessive,
The polarity of liquid phase solvent will be changed, cause the solubility of acetylene and CO gases to decline, acrylic acid selectivity reduction, yield drop
It is low.
Embodiments in accordance with the present invention, the addition of catalyst is not particularly restricted, and those skilled in the art can root
Selected according to being actually needed, according to a particular embodiment of the invention, the addition (quality) of catalyst can be organic solvent
With the 0.1~10% of water gross mass.When catalyst amount is very few, reactivity is not high；When catalyst amount is excessive, reaction yield
Do not improved with increasing for catalytic amount, the specific activity of reaction declines.
S200：Obtain acrylic products
In the step, acetylene and carbon monoxide are passed through into autoclave, and make catalyst acetylene, carbon monoxide and water
React, to obtain acrylic acid.
Specifically, before acetylene and carbon monoxide are passed through into autoclave, 1MPa nitrogen displacement autoclaves can first be used
Interior air 2 times, to remove air in autoclave, it is possible thereby to further improve the yield of acrylic acid.Further, in stirring
Under the conditions of, acetylene is passed through into autoclave to certain pressure (such as 0.2MPa), then be passed through carbon monoxide to certain pressure (such as 4~
6MPa), then reaction system is heated up, to obtain acrylic acid product.
According to the specific embodiment of the present invention, raw material acetylene and carbon monoxide need not be pre-processed, Ke Yizhi
Connect for acrylic acid synthesizing.The catalyst system of the present invention is high to the impurity tolerance level in unstrpped gas, and especially acetylene gas is not
Need by purified treatments such as extra desulfurization dephosphorizations, because being free of noble metal in the catalyst composition of the present invention, therefore
Tolerance to poisonous substances such as sulphur, phosphorus is high.
According to a particular embodiment of the invention, the mol ratio of acetylene and carbon monoxide can be 1:(1~15).Thus, may be used
Further to improve the yield of acrylic acid.
Embodiments in accordance with the present invention, the temperature of above-mentioned reaction is not particularly restricted, and those skilled in the art can root
Selected according to being actually needed, according to a particular embodiment of the invention, above-mentioned reaction can be in 170~230 degrees Celsius of temperature
Lower completion.Thus, it is possible to further improve the yield of acrylic acid.
Embodiments in accordance with the present invention, the pressure of above-mentioned reaction is not particularly restricted, and those skilled in the art can root
Selected according to being actually needed, according to a particular embodiment of the invention, above-mentioned reaction can be completed under 5~11MPa pressure
's.Thus, it is possible to further improve the yield of acrylic acid.
Embodiments in accordance with the present invention, the time of the progress of above-mentioned reaction is not particularly restricted, those skilled in the art
It can be selected according to actual needs, according to a particular embodiment of the invention, it is complete that above-mentioned reaction can carry out 25~120min
Into.Inventor has found that the reaction time is too short, and acetylene has little time complete conversion, and acrylic acid yield is not high, and further increases anti-
Between seasonable, the yield of acrylic acid is basically unchanged.
Thus, it is according to embodiments of the present invention prepare acrylic acid by using production cost it is low, stability, urge
Change the high catalyst acetylene of activity and selectivity and carbon monoxide and water reaction generation acrylic acid, so as to inexpensive high
Yield prepares acrylic acid, and the present invention the catalyst that is used of method for heterogeneous catalysis, be easy to and target
Product is separated, and is had broad application prospects.
Below with reference to specific embodiment, present invention is described, it is necessary to which explanation, these embodiments are only description
Property, without limiting the present invention in any way.
Embodiment 1
Weigh Ni (CH3COO)2·4H2O 0.50g, CuBr20.23g, Y molecular sieve 0.1g are dissolved in 97mL THF and 12mL
H2In O, add in 500mL autoclaves, use 1MPa N2Air 2 times in kettle are replaced, C is filled2H20.2MPa is saturated to, CO is then filled extremely
4.5MPa, is warming up to 200 DEG C, under speed of agitator 1000rpm, reacts 1.5 hours.Reaction is entered after terminating to tail gas and reaction solution
Row is analyzed, after testing C2H2Conversion ratio is 95%, and the yield of acrylic acid is 79%.
Embodiment 2
Weigh NiO 0.50g, CuCl20.27g, ZSM-5 molecular sieve 0.1g is dissolved in 100mL acetone and 12mL H2In O, plus
Enter in 500mL autoclaves, use 1MPa N2Air 2 times in kettle are replaced, C is filled2H20.3MPa is saturated to, CO to 5MPa is then filled, risen
Temperature is reacted 1 hour to 200 DEG C.Reaction is analyzed tail gas and reaction solution after terminating, after testing C2H2Conversion ratio is 90%, third
The yield of olefin(e) acid is 82%.
Embodiment 3
Weigh Ni2O30.50g, CuI20.95g, beta-molecular sieve 0.1g is dissolved in 100mL 1-METHYLPYRROLIDONEs and 12mL
H2In O, add in 500mL autoclaves, use 1MPa N2Air 2 times in kettle are replaced, C is filled2H20.3MPa is saturated to, CO is then filled extremely
5MPa, is warming up to 220 DEG C, reacts 0.5 hour.Reaction is analyzed tail gas and reaction solution after terminating, after testing C2H2Conversion ratio
For 92%, the yield of acrylic acid is 85%.
Embodiment 4
Weigh NiSO41.00g, CuI20.95g, SAPO-11 molecular sieve 0.15g are dissolved in 100mL N, N- dimethyl formyls
Amine and 12mL H2In O, add in 500mL autoclaves, use 1MPa N2Air 2 times in kettle are replaced, C is filled2H2It is saturated to 0.3MPa,
Then CO is filled to 6MPa, 190 DEG C are warming up to, and is reacted 0.5 hour.Reaction is analyzed tail gas and reaction solution after terminating, through inspection
Survey C2H2Conversion ratio is 90%, and the yield of acrylic acid is 84%.
Embodiment 5
Weigh NiO 0.15g, CuBr20.22g, X-type molecular sieve 0.05g be dissolved in 100mL DMFs and
12mL H2In O, add in 500mL autoclaves, use 1MPa N2Air 2 times in kettle are replaced, C is filled2H20.3MPa is saturated to, then
CO is filled to 4MPa, 220 DEG C are warming up to, and is reacted 1.5 hours.Reaction is analyzed tail gas and reaction solution after terminating, after testing C2H2
Conversion ratio is 95%, and the yield of acrylic acid is 85%.
Embodiment 6
Using 2- methyltetrahydrofurans as solvent, Ni Br are weighed21.03g, CuBr20.53g, 0.2g A type molecules
Sieve, other condition be the same as Examples 1, C2H2Conversion ratio is 89%, and the yield of acrylic acid is 76%.
Embodiment 7
Using 0.5g nickel nitrates, 0.1g ZSM-22 molecular sieves, other condition be the same as Examples 2, C2H2Conversion ratio is 87%, third
The yield of olefin(e) acid is 80%.
Embodiment 8
Using 0.5g nickel hydroxides, 0.1g SAPO-34 molecular sieves, other condition be the same as Examples 3, C2H2Conversion ratio is
93%, the yield of acrylic acid is 83%.
In the description of this specification, reference term " one embodiment ", " some embodiments ", " example ", " specifically show
The description of example " or " some examples " etc. means to combine specific features, structure, material or the spy that the embodiment or example are described
Point is contained at least one embodiment of the present invention or example.In this manual, to the schematic representation of above-mentioned term not
Identical embodiment or example must be directed to.Moreover, specific features, structure, material or the feature of description can be with office
Combined in an appropriate manner in one or more embodiments or example.In addition, in the case of not conflicting, the skill of this area
Art personnel can be tied the not be the same as Example or the feature of example and non-be the same as Example or example described in this specification
Close and combine.
Although embodiments of the invention have been shown and described above, it is to be understood that above-described embodiment is example
Property, it is impossible to limitation of the present invention is interpreted as, one of ordinary skill in the art within the scope of the invention can be to above-mentioned
Embodiment is changed, changed, replacing and modification.
Claims (10)
1. one kind prepares acrylic acid, it is characterised in that including：
Catalyst is mixed with organic solvent and water in autoclave；
Acetylene and carbon monoxide are passed through into the autoclave, and makes acetylene, carbon monoxide and water described in the catalyst
React, to obtain acrylic acid,
Wherein, the catalyst includes nickel compound containing, copper halide and molecular sieve,
Nickel ion and Cu in the copper halide in the nickel compound containing2+Mol ratio be (2~5):1,
The quality of the molecular sieve is the 0.1~20% of the nickel compound containing and the halogenation copper mass summation.
2. acrylic acid is prepared according to claim 1, it is characterised in that the nickel compound containing is the halogenation of nickel
One kind in thing, sulfate, acetate, nitrate, hydroxide and oxide.
3. prepare acrylic acid according to claim 1, it is characterised in that the molecular sieve include selected from beta-molecular sieve,
At least one of A type molecular sieve, X-type molecular sieve, Y type molecular sieve, ZSM-5, ZSM-22, SAPO-34 and SAPO-11.
4. acrylic acid is prepared according to claim 1, it is characterised in that the organic solvent includes being selected from tetrahydrochysene furan
Mutter, at least one of 2- methyltetrahydrofurans, acetone, 1-METHYLPYRROLIDONE, N,N-dimethylformamide.
5. acrylic acid is prepared according to claim 1, it is characterised in that the quality of the water is the organic solvent
The 10~25% of quality.
6. acrylic acid is prepared according to claim 1, it is characterised in that the quality of the catalyst is described organic
The 0.1~10% of solvent and the water gross mass.
7. acrylic acid is prepared according to claim 1, it is characterised in that the acetylene rubs with the carbon monoxide
You are than being 1:(1~15).
8. acrylic acid is prepared according to claim 1, it is characterised in that the reaction is at 170~230 degrees Celsius
At a temperature of complete.
9. acrylic acid is prepared according to claim 1, it is characterised in that the reaction is the pressure in 5~11MPa
Lower completion.
10. acrylic acid is prepared according to claim 1, it is characterised in that the reaction is 25~120min of carry out
Complete.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110152694A (en) * | 2019-06-21 | 2019-08-23 | 石河子大学 | A kind of heterogeneous acetylene carbonylating catalyst and preparation method thereof, application |
| CN114874088A (en) * | 2022-06-06 | 2022-08-09 | 中国科学院上海高等研究院 | Acetylenic acid and preparation method thereof |
-
2017
- 2017-05-09 CN CN201710322606.0A patent/CN107118093B/en active Active
Non-Patent Citations (1)
| Title |
|---|
| 林铁军: "镍基催化剂的乙炔氢羧基化合成丙烯酸性能研究", 《中国博士学位论文全文数据库 工程科技I辑》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110152694A (en) * | 2019-06-21 | 2019-08-23 | 石河子大学 | A kind of heterogeneous acetylene carbonylating catalyst and preparation method thereof, application |
| CN110152694B (en) * | 2019-06-21 | 2022-03-22 | 石河子大学 | Heterogeneous acetylene carbonylation catalyst and preparation method and application thereof |
| CN114874088A (en) * | 2022-06-06 | 2022-08-09 | 中国科学院上海高等研究院 | Acetylenic acid and preparation method thereof |
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