CN109012751A - A kind of application with Cabbeen-palladium structure catalyst and its in selective hydrogenation of acetylene reaction - Google Patents
A kind of application with Cabbeen-palladium structure catalyst and its in selective hydrogenation of acetylene reaction Download PDFInfo
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- CN109012751A CN109012751A CN201810942072.6A CN201810942072A CN109012751A CN 109012751 A CN109012751 A CN 109012751A CN 201810942072 A CN201810942072 A CN 201810942072A CN 109012751 A CN109012751 A CN 109012751A
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- palladium
- cabbeen
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- 239000003054 catalyst Substances 0.000 title claims abstract description 63
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 title claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 23
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 18
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 166
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 113
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 85
- 239000007788 liquid Substances 0.000 claims abstract description 19
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims abstract description 17
- 229940040526 anhydrous sodium acetate Drugs 0.000 claims abstract description 17
- 239000002608 ionic liquid Substances 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 12
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000002360 preparation method Methods 0.000 claims abstract description 7
- 150000002500 ions Chemical class 0.000 claims abstract description 3
- 239000000843 powder Substances 0.000 claims abstract description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 39
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 30
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 9
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- -1 Glyoxaline cation Chemical class 0.000 claims description 4
- 150000001450 anions Chemical class 0.000 claims description 4
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- JKDRQYIYVJVOPF-FDGPNNRMSA-L palladium(ii) acetylacetonate Chemical compound [Pd+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O JKDRQYIYVJVOPF-FDGPNNRMSA-L 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 2
- 229940006460 bromide ion Drugs 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 claims description 2
- 229940006461 iodide ion Drugs 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 238000009210 therapy by ultrasound Methods 0.000 claims description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 2
- 239000000460 chlorine Substances 0.000 claims 2
- 229910052801 chlorine Inorganic materials 0.000 claims 2
- UNEATYXSUBPPKP-UHFFFAOYSA-N 1,3-Diisopropylbenzene Chemical class CC(C)C1=CC=CC(C(C)C)=C1 UNEATYXSUBPPKP-UHFFFAOYSA-N 0.000 claims 1
- VPUAYOJTHRDUTK-UHFFFAOYSA-N 1-ethylpyrrole Chemical class CCN1C=CC=C1 VPUAYOJTHRDUTK-UHFFFAOYSA-N 0.000 claims 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 1
- 150000001768 cations Chemical class 0.000 claims 1
- 239000011591 potassium Substances 0.000 claims 1
- 229910052700 potassium Inorganic materials 0.000 claims 1
- 238000011084 recovery Methods 0.000 claims 1
- 238000003756 stirring Methods 0.000 abstract description 23
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 20
- 239000005977 Ethylene Substances 0.000 abstract description 20
- 238000007654 immersion Methods 0.000 abstract description 8
- 150000001345 alkine derivatives Chemical class 0.000 abstract description 2
- 238000001035 drying Methods 0.000 abstract 1
- 238000002803 maceration Methods 0.000 description 50
- 238000000034 method Methods 0.000 description 22
- 238000010438 heat treatment Methods 0.000 description 17
- 238000001802 infusion Methods 0.000 description 17
- 239000007787 solid Substances 0.000 description 17
- 238000002604 ultrasonography Methods 0.000 description 17
- 238000009736 wetting Methods 0.000 description 17
- 238000005660 chlorination reaction Methods 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 150000001805 chlorine compounds Chemical class 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000002386 leaching Methods 0.000 description 3
- 239000012495 reaction gas Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- IWDFHWZHHOSSGR-UHFFFAOYSA-N 1-ethylimidazole Chemical class CCN1C=CN=C1 IWDFHWZHHOSSGR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910021124 PdAg Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003708 ampul Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002941 palladium compounds Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000012985 polymerization agent Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
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- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0203—Impregnation the impregnation liquid containing organic compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0213—Preparation of the impregnating solution
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/08—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds
- C07C5/09—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds to carbon-to-carbon double bonds
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The invention discloses a kind of applications with Cabbeen-palladium structure catalyst and its in selective hydrogenation of acetylene reaction.The catalyst includes alumina support and Cabbeen-palladium for being supported on carrier, and the catalyst passes through the preparation method included the following steps and is made: (1) in a solvent by ion liquid dissolving, obtaining ionic liquid solution;(2) powder potassium tert-butoxide or anhydrous sodium acetate are added into ionic liquid solution, stirs 1-3h at 60-150 DEG C to get Cabbeen solution is arrived;(3) palladium presoma is proportionally added in Cabbeen solution, stirs to get containing Cabbeen-palladium solution;(4) equably alumina support is poured into containing aluminium oxide is totally submerged and fully dispersed, the carrier room temperature immersion soaked by solution, then drying is obtained with Cabbeen-palladium structure catalyst.Catalyst of the present invention is applied in selective hydrogenation of acetylene reaction, has the characteristics that conversion of alkyne, ethylene selectivity are high.
Description
(1) technical field
The present invention relates to a kind of with Cabbeen-palladium structure catalyst and its in preparing ethylene by selective hydrogenation of acetylene reaction
Application.
(2) technical background
Ethylene is widely used in every field as important Organic Chemicals.The resulting ethylogen of industrial production
Expect gas in, often containing 1% acetylene.The trace acetylene mixed in ethylene raw material gas can poison urging for subsequent ethylene polymerization
Agent, and reduce the quality of polyethylene product.Therefore, the acetylene in unstripped gas is removed to 5ppm or less and is of great significance.
Frequently with the acetylene in solvent absorption, selective hydrogenation method removing ethylene raw in ethylene unit.It is inhaled with solvent
Receipts method is compared, and catalysis selective hydrogenation compares absorption process, and pollution is small, while removing acetylene impurities, moreover it is possible to improve the production of ethylene
Amount.However traditional catalyst used by industrial, when acetylene is in high conversion, the selectivity of ethylene is very low.This is because
Ethylene is not desorbed in time during the reaction, caused by excessive hydrogenation.
Therefore, how to design the selective hydrocatalyst of acetylene that ethylene can be promoted to be desorbed has for improving selectivity
Significance.Document (the .Promotional effect ofPd single atoms such as PEI G X onAu
nanoparticles supported on silica for the selective hydrogenation of
Acetylene in excess ethylene [J] .New Journal of Chemistry, 2014,38 (5): 2043-
2051.ZHOU H R etc., Pd/ZnO catalysts with different origins for high
chemoselectivity in acetylene semi-hydrogenation[J].Chinese Journal
OfCatalysis, 2016,37 (5): 692-699.) disclosure report, the small palladium particle of partial size is prepared, can effectively reduce ethylene
Adsorption strength;Furthermore document (Liu Y etc., Highly efficient PdAg catalyst using a reducible
Mg-Ti mixed oxide for selective hydrogenation of acetylene:Role of acidic and
Basic sites [J] .Journal of Catalysis, 2017,348:135-145.Kim E etc., Pd catalyst
promoted by two metal oxides with different reducibilities:Properties and
performance in the selective hydrogenation ofacetylene☆[J].Applied Catalysis
A General, 2014,471 (5): 80-83.) it points out again, the cloud density of palladium is improved, the desorption of ethylene can be promoted.
Based on background above, the invention proposes small with a kind of partial size, the high palladium activated centre of cloud density is urged
The preparation method of agent, the catalyst can obtain preferable acetylene reaction activity, and the ethylene choosing that reaction obtains at low temperature
Selecting property is high, good stability.
(3) summary of the invention
The purpose of the present invention is to provide a kind of with Cabbeen-palladium structure catalyst and its anti-in selective hydrogenation of acetylene
Application in answering, the catalyst have the characteristics that conversion of alkyne, ethylene selectivity are high.
Technical solution used in the present invention is illustrated below.
On the one hand, the present invention provides a kind of with Cabbeen-palladium structure catalyst, including alumina support and is supported on
Cabbeen-palladium on carrier, the catalyst pass through the preparation method included the following steps and are made:
(1) in a solvent by ion liquid dissolving, ionic liquid solution is obtained;The ionic liquid is with -3 methyl of 1- ethyl
Imidazoles, -3 methylimidazole of 1- propyl, -3 methylimidazole of 1- butyl, -3 methylimidazole of 1- amyl or bis- (the 2,6- diisopropyls of 1,3-
Benzene) glyoxaline cation is cationic, using chloride ion, bromide ion or iodide ion as anion;The solvent is selected from tetrahydrofuran
(THF), one of N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO);
(2) powder potassium tert-butoxide or anhydrous sodium acetate are added into ionic liquid solution, at 60-150 DEG C (preferably 90 DEG C)
Lower stirring 1-3h is completely dissolved solid to get Cabbeen solution is arrived;
(3) palladium presoma is proportionally added in Cabbeen solution, the palladium presoma is palladium acetate, palladium acetylacetonate
Or dichloro diamino palladium, and 2-4h (preferably 4h) is stirred under 60-150 DEG C (preferably 120 DEG C), it obtains containing Cabbeen-palladium solution;
(4) equably alumina support is poured into containing in Cabbeen-palladium solution, aluminium oxide is made to be totally submerged and be filled by solution
Dispersion, the carrier soaked impregnate 8-14h (preferably 12h) at room temperature, then dry under 110-130 DEG C (preferably 110 DEG C)
8-14h (12h) is obtained with Cabbeen-palladium structure catalyst.
The preparation method of catalyst of the present invention, Cabbeen-palladium are regarded as whole loads, and those skilled in the art can be with
The additional amount of load capacity selection palladium compound and ionic liquid as needed.Preferably there is Cabbeen-palladium structure in the present invention
The load capacity (i.e. the mass percent of palladium and carrier) of palladium is 0.04-0.2wt% in catalyst.
In the preparation of catalyst of the present invention, the ionic liquid, potassium tert-butoxide or anhydrous sodium acetate, palladium presoma
Molar ratio is 1:1-1.2:0.5-2.The ionic liquid is preferably using chloride ion as anion;Most preferably ionic liquid is
- 3 methylimidazole of chlorination 1- propyl.The solvent is preferably DMF.The palladium presoma is preferably palladium acetate.
In the present invention, the specific surface area of alumina support is preferably 58-420m2/g。
In step (4) of the present invention, if the aluminium oxide of addition can not be submerged containing Cabbeen-palladium solution, it can be added a certain amount of
Solvent is completely submerged aluminium oxide.
In step (4) of the present invention, after aluminium oxide is added, preferably make aluminium oxide containing Cabbeen-palladium solution by ultrasonic treatment
In be uniformly dispersed.
On the other hand, the present invention provides described there is Cabbeen-palladium structure catalyst to react in selective hydrogenation of acetylene
In application first catalyst is restored with hydrogen before application, reduction temperature be 60-150 DEG C (preferably 100 DEG C), reduction
Time is 1-3h.
Further, the condition of selective hydrogenation of acetylene is: reaction temperature is 50-160 DEG C (preferably 70-80 DEG C), reaction pressure
Power is 0.1-1MPa (preferably normal pressure), air speed 4000-15000h-1。
Compared with prior art, the beneficial effects of the present invention are:
(1) what is be prepared in the present invention has Cabbeen-palladium structure catalyst, and palladium nano-particles partial size is small, palladium electronics
Cloud density is high, which can promote the desorption of ethylene in reaction process, to substantially increase the choosing of ethylene in the reaction
Selecting property.
(2) produced by the present invention that there is Cabbeen-palladium structure catalyst can obtain preferably at low temperature (70-80 DEG C)
Acetylene reaction activity, and the ethylene selectivity that reaction obtains is high.
(4) Detailed description of the invention
Fig. 1 is scanning transmission electron microscope (STEM) photo of embodiment 7, is prepared as seen from the figure by this method
Catalyst metals partial size it is small, it is scattered.
(5) specific embodiment
Illustrate the present invention with specific example below.It is important to point out that embodiment is served only for carrying out the present invention
It further illustrates, but should not be understood as limiting the scope of the invention.
Embodiment 1
Claim -3 methylimidazole of 0.08g (0.5mmol) chlorination 1- propyl to be dissolved in 2mL dimethyl sulfoxide (DMSO), and is added
Anhydrous sodium acetate 0.041g (0.5mmol), 90 DEG C of constant temperature stirring holding 1h to solid are completely dissolved, then are added into clear solution
0.22g (1.0mmol) palladium acetate is as palladium presoma, and 120 DEG C of agitating and heating 4h are to get Cabbeen-palladium solution.Acquired solution is turned
It moves in 10mL volumetric flask, adds DMSO to corresponding scale, obtain Cabbeen-palladium steeping liq that concentration is 0.001g/mL.
Using infusion process, Cabbeen-palladium maceration extract of metering is pipetted, and certain DMSO is added and is mixed with maceration extract, then
Evenly by alumina support (specific surface area 384m2/ g) pour into maceration extract, and ultrasound.By the aluminium oxide of wetting in room temperature immersion
12h, and the dry 12h at 110 DEG C, obtaining palladium load capacity is 0.1wt% with Cabbeen-palladium structure catalyst.
Embodiment 2
Claim -3 methylimidazole of 0.16g (1.0mmol) chlorination 1- propyl to be dissolved in 2mL dimethyl sulfoxide (DMSO), and is added
Anhydrous sodium acetate 0.082g (1.0mmol), 90 DEG C of constant temperature stirring holding 1h to solid are completely dissolved, then are added into clear solution
0.22g (1.0mmol) palladium acetate is as palladium presoma, and 120 DEG C of agitating and heating 4h are to get Cabbeen-palladium solution.Acquired solution is turned
It moves in 10mL volumetric flask, adds DMSO to corresponding scale, obtain Cabbeen-palladium steeping liq that concentration is 0.001g/mL.
Using infusion process, Cabbeen-palladium maceration extract of metering is pipetted, and certain DMSO is added and is mixed with maceration extract, then
Evenly by alumina support (specific surface area 384m2/ g) pour into maceration extract, and ultrasound.By the aluminium oxide of wetting in room temperature immersion
12h, and the dry 12h at 110 DEG C, obtaining palladium load capacity is 0.1wt% with Cabbeen-palladium structure catalyst.
Embodiment 3
Claim -3 methylimidazole of 0.32g (2.0mmol) chlorination 1- propyl to be dissolved in 2mL dimethyl sulfoxide (DMSO), and is added
Anhydrous sodium acetate 0.16g (2.0mmol), 90 DEG C of constant temperature stirring holding 1h to solid are completely dissolved, then are added into clear solution
0.22g (1.0mmol) palladium acetate is as palladium presoma, and 120 DEG C of agitating and heating 4h are to get Cabbeen-palladium solution.Acquired solution is turned
It moves in 10mL volumetric flask, adds DMSO to corresponding scale, obtain Cabbeen-palladium steeping liq that concentration is 0.001g/mL.
Using infusion process, Cabbeen-palladium maceration extract of metering is pipetted, and certain DMSO is added and is mixed with maceration extract, then
Evenly by alumina support (specific surface area 384m2/ g) pour into maceration extract, and ultrasound.By the aluminium oxide of wetting in room temperature immersion
12h, and the dry 12h at 110 DEG C, obtaining palladium load capacity is 0.1wt% with Cabbeen-palladium structure catalyst.
Embodiment 4
- 3 methylimidazole of 0.32g (2.0mmol) chlorination 1- propyl is claimed to be dissolved in 2mL n,N-Dimethylformamide (DMF),
And anhydrous sodium acetate 0.16g (2.0mmol) is added, the stirring of 90 DEG C of constant temperature keeps 1h to be completely dissolved to solid, then to clear solution
Middle addition 0.22g (1.0mmol) palladium acetate is as palladium presoma, and 120 DEG C of agitating and heating 4h are to get Cabbeen-palladium solution.By gained
Solution is transferred in 10mL volumetric flask, is added DMF to corresponding scale, is obtained Cabbeen-palladium steeping liq that concentration is 0.001g/mL.
Using infusion process, Cabbeen-palladium maceration extract of metering is pipetted, and certain DMF is added and is mixed with maceration extract, then uniformly
Ground is by alumina support (specific surface area 384m2/ g) pour into maceration extract, and ultrasound.By the aluminium oxide of wetting in room temperature immersion
12h, and the dry 12h at 110 DEG C, obtaining palladium load capacity is 0.1wt% with Cabbeen-palladium structure catalyst.
Embodiment 5
Bis- (2, the 6- diisopropyl benzene) imidazolitm chlorides of 0.21g (0.5mmol) 1,3- are claimed to be dissolved in 4mLN, N- dimethyl formyl
In amine (DMF), and potassium tert-butoxide 0.06g (0.6mmol) being added, 90 DEG C of constant temperature stirring holding 1h to solid are completely dissolved, then to
0.22g (1.0mmol) palladium acetate is added in clear solution as palladium presoma, 120 DEG C of agitating and heating 4h are molten to get Cabbeen-palladium
Liquid.Acquired solution is transferred in 10mL volumetric flask, adds DMF to corresponding scale, obtains Cabbeen-palladium leaching that concentration is 0.001g/mL
Stain liquid.
Using infusion process, Cabbeen-palladium maceration extract of metering is pipetted, and certain DMF is added and is mixed with maceration extract, then uniformly
By alumina support (specific surface area 384m2/ g) pour into maceration extract, and ultrasound.The Supported alumina of wetting is soaked in room temperature
Stain 12h, and the dry 12h at 110 DEG C, obtaining palladium load capacity is 0.1wt% with Cabbeen-palladium structure catalyst.
Embodiment 6
Bis- (2, the 6- diisopropyl benzene) imidazolitm chlorides of 0.43g (1.0mmol) 1,3- are claimed to be dissolved in 4mLN, N- dimethyl formyl
In amine (DMF), and potassium tert-butoxide 0.12g (1.1mmol) being added, 90 DEG C of constant temperature stirring holding 1h to solid are completely dissolved, then to
0.22g (1.0mmol) palladium acetate is added in clear solution as palladium presoma, 120 DEG C of agitating and heating 4h are molten to get Cabbeen-palladium
Liquid.Acquired solution is transferred in 10mL volumetric flask, adds DMF to corresponding scale, obtains Cabbeen-palladium leaching that concentration is 0.001g/mL
Stain liquid.
Using infusion process, Cabbeen-palladium maceration extract of metering is pipetted, and certain DMF is added and is mixed with maceration extract, then uniformly
By alumina support (specific surface area 384m2/ g) pour into maceration extract, and ultrasound.The Supported alumina of wetting is soaked in room temperature
Stain 12h, and the dry 12h at 110 DEG C, obtaining palladium load capacity is 0.1wt% with Cabbeen-palladium structure catalyst.
Embodiment 7
Bis- (2, the 6- diisopropyl benzene) imidazolitm chlorides of 0.85g (2.0mmol) 1,3- are claimed to be dissolved in 4mLN, N- dimethyl formyl
In amine (DMF), and potassium tert-butoxide 0.24g (2.1mmol) being added, 90 DEG C of constant temperature stirring holding 1h to solid are completely dissolved, then to
0.22g (1.0mmol) palladium acetate is added in clear solution as palladium presoma, 120 DEG C of agitating and heating 4h are molten to get Cabbeen-palladium
Liquid.Acquired solution is transferred in 10mL volumetric flask, adds DMF to corresponding scale, obtains Cabbeen-palladium leaching that concentration is 0.001g/mL
Stain liquid.
Using infusion process, Cabbeen-palladium maceration extract of metering is pipetted, and certain DMF is added and is mixed with maceration extract, then uniformly
By alumina support (specific surface area 384m2/ g) pour into maceration extract, and ultrasound.The Supported alumina of wetting is soaked in room temperature
Stain 12 hours, and the dry 12h at 110 DEG C, obtaining palladium load capacity is 0.1wt% with Cabbeen-palladium structure catalyst.
Embodiment 8
Bis- (2, the 6- diisopropyl benzene) imidazolitm chlorides of 0.85g (2.0mmol) 1,3- are claimed to be dissolved in 4mLN, N- dimethyl formyl
In amine (DMF), and potassium tert-butoxide 0.24g (2.1mmol) being added, 90 DEG C of constant temperature stirring holding 1h to solid are completely dissolved, then to
0.30g (1.0mmol) palladium acetylacetonate is added in clear solution as palladium presoma, 120 DEG C of agitating and heating 4h are to get Cabbeen-
Palladium solution.Acquired solution is transferred in 10mL volumetric flask, adds DMF to corresponding scale, obtains the Cabbeen-that concentration is 0.001g/mL
Palladium steeping liq.
Using infusion process, Cabbeen-palladium maceration extract of metering is pipetted, and certain DMF is added and is mixed with maceration extract, then uniformly
By alumina support (specific surface area 384m2/ g) pour into maceration extract, and ultrasound.The Supported alumina of wetting is soaked in room temperature
Stain 12h, and the dry 12h at 110 DEG C, obtaining palladium load capacity is 0.1wt% with Cabbeen-palladium structure catalyst.
Embodiment 9
- 3 methylimidazole of 0.41g (2.0mmol) bromination 1- propyl is claimed to be dissolved in 2mL n,N-Dimethylformamide (DMF),
And anhydrous sodium acetate 0.16g (2.0mmol) is added, the stirring of 90 DEG C of constant temperature keeps 1h to be completely dissolved to solid, then to clear solution
Middle addition 0.22g (1.0mmol) palladium acetate is as presoma, and 120 DEG C of agitating and heating 4h are to get Cabbeen-palladium solution.Gained is molten
Liquid is transferred in 10mL volumetric flask, is added DMF to corresponding scale, is obtained Cabbeen-palladium steeping liq that concentration is 0.001g/mL.
Using infusion process, Cabbeen-palladium maceration extract of metering is pipetted, and certain DMF is added and is mixed with maceration extract, then uniformly
By alumina support (specific surface area 384m2/ g) pour into maceration extract, and ultrasound.The Supported alumina of wetting is soaked in room temperature
Stain 12h, and the dry 12h at 110 DEG C, obtaining palladium load capacity is 0.1wt% with Cabbeen-palladium structure catalyst.
Embodiment 10
- 3 methylimidazole of 0.50g (2.0mmol) iodate 1- propyl is claimed to be dissolved in 2mL n,N-Dimethylformamide (DMF),
And anhydrous sodium acetate 0.16g (2.0mmol) is added, the stirring of 90 DEG C of constant temperature keeps 1h to be completely dissolved to solid, then to clear solution
Middle addition 0.22g (1.0mmol) palladium acetate is as presoma, and 120 DEG C of agitating and heating 4h are to get Cabbeen-palladium solution.Gained is molten
Liquid is transferred in 10mL volumetric flask, is added DMF to corresponding scale, is obtained Cabbeen-palladium steeping liq that concentration is 0.001g/mL.
Using infusion process, Cabbeen-palladium maceration extract of metering is pipetted, and certain DMF is added and is mixed with maceration extract, then uniformly
By alumina support (specific surface area 384m2/ g) pour into maceration extract, and ultrasound.The Supported alumina of wetting is soaked in room temperature
Stain 12h, and the dry 12h at 110 DEG C, obtaining palladium load capacity is 0.1wt% with Cabbeen-palladium structure catalyst.
Embodiment 11
- 3 methylimidazole of 0.29g (2.0mmol) chlorination 1- ethyl is claimed to be dissolved in 2mL n,N-Dimethylformamide (DMF),
And anhydrous sodium acetate 0.16g (2.0mmol) is added, the stirring of 90 DEG C of constant temperature keeps 1h to be completely dissolved to solid, then to clear solution
Middle addition 0.22g (1.0mmol) palladium acetate is as presoma, and 120 DEG C of agitating and heating 4h are to get Cabbeen-palladium solution.Gained is molten
Liquid is transferred in 10mL volumetric flask, is added DMF to corresponding scale, is obtained Cabbeen-palladium steeping liq that concentration is 0.001g/mL.
Using infusion process, Cabbeen-palladium maceration extract of metering is pipetted, and certain DMF is added and is mixed with maceration extract, then uniformly
By alumina support (specific surface area 384m2/ g) pour into maceration extract, and ultrasound.The Supported alumina of wetting is soaked in room temperature
Stain 12h, and the dry 12h at 110 DEG C, obtaining palladium load capacity is 0.1wt% with Cabbeen-palladium structure catalyst.
Embodiment 12
0.35g (2.0mmol) 1-butyl-3-methylimdazoliuim chloride is claimed to be dissolved in 2mL n,N-Dimethylformamide (DMF),
And anhydrous sodium acetate 0.16g (2.0mmol) is added, the stirring of 90 DEG C of constant temperature keeps 1h to be completely dissolved to solid, then to clear solution
Middle addition 0.22g (1.0mmol) palladium acetate is as presoma, and 120 DEG C of agitating and heating 4h are to get Cabbeen-palladium solution.Gained is molten
Liquid is transferred in 10mL volumetric flask, is added DMF to corresponding scale, is obtained Cabbeen-palladium steeping liq that concentration is 0.001g/mL.
Using infusion process, Cabbeen-palladium maceration extract of metering is pipetted, and certain DMF is added and is mixed with maceration extract, then uniformly
By alumina support (specific surface area 384m2/ g) pour into maceration extract, and ultrasound.The Supported alumina of wetting is soaked in room temperature
Stain 12h, and the dry 12h at 110 DEG C, obtaining palladium load capacity is 0.1wt% with Cabbeen-palladium structure catalyst.
Embodiment 13
0.35g (2.0mmol) 1-butyl-3-methylimdazoliuim chloride is claimed to be dissolved in 2mL n,N-Dimethylformamide (DMF),
And anhydrous sodium acetate 0.16g (2.0mmol) is added, the stirring of 90 DEG C of constant temperature keeps 1h to be completely dissolved to solid, then to clear solution
Middle addition 0.22g (1.0mmol) palladium acetate is as presoma, and 120 DEG C of agitating and heating 4h are to get Cabbeen-palladium solution.Gained is molten
Liquid is transferred in 10mL volumetric flask, is added DMF to corresponding scale, is obtained Cabbeen-palladium steeping liq that concentration is 0.001g/mL.
Using infusion process, Cabbeen-palladium maceration extract of metering is pipetted, and certain DMF is added and is mixed with maceration extract, then uniformly
By alumina support (specific surface area 58m2/ g) pour into maceration extract, and ultrasound.The Supported alumina of wetting is soaked in room temperature
Stain 12h, and the dry 12h at 110 DEG C, obtaining palladium load capacity is 0.1wt% with Cabbeen-palladium structure catalyst.
Embodiment 14
0.35g (2.0mmol) 1-butyl-3-methylimdazoliuim chloride is claimed to be dissolved in 2mL n,N-Dimethylformamide (DMF),
And anhydrous sodium acetate 0.16g (2.0mmol) is added, the stirring of 90 DEG C of constant temperature keeps 1h to be completely dissolved to solid, then to clear solution
Middle addition 0.22g (1.0mmol) palladium acetate is as presoma, and 120 DEG C of agitating and heating 4h are to get Cabbeen-palladium solution.Gained is molten
Liquid is transferred in 10mL volumetric flask, is added DMF to corresponding scale, is obtained Cabbeen-palladium steeping liq that concentration is 0.001g/mL.
Using infusion process, Cabbeen-palladium maceration extract of metering is pipetted, and certain DMF is added and is mixed with maceration extract, then uniformly
By alumina support (specific surface area 420m2/ g) pour into maceration extract, and ultrasound.The Supported alumina of wetting is soaked in room temperature
Stain 12h, and the dry 12h at 110 DEG C, obtaining palladium load capacity is 0.1wt% with Cabbeen-palladium structure catalyst.
Embodiment 15
0.35g (2.0mmol) 1-butyl-3-methylimdazoliuim chloride is claimed to be dissolved in 2mL n,N-Dimethylformamide (DMF),
And anhydrous sodium acetate 0.16g (2.0mmol) is added, the stirring of 90 DEG C of constant temperature keeps 1h to be completely dissolved to solid, then to clear solution
Middle addition 0.22g (1.0mmol) palladium acetate is as presoma, and 120 DEG C of agitating and heating 4h are to get Cabbeen-palladium solution.Gained is molten
Liquid is transferred in 5mL volumetric flask, is added DMF to corresponding scale, is obtained Cabbeen-palladium steeping liq that concentration is 0.002g/mL.
Using infusion process, Cabbeen-palladium maceration extract of metering is pipetted, and certain DMF is added and is mixed with maceration extract, then uniformly
By alumina support (specific surface area 420m2/ g) pour into maceration extract, and ultrasound.The Supported alumina of wetting is soaked in room temperature
Stain 12h, and the dry 12h at 110 DEG C, obtaining palladium load capacity is 0.2wt% with Cabbeen-palladium structure catalyst.
Embodiment 16
0.35g (2.0mmol) 1-butyl-3-methylimdazoliuim chloride is claimed to be dissolved in 2mL n,N-Dimethylformamide (DMF),
And anhydrous sodium acetate 0.16g (2.0mmol) is added, the stirring of 90 DEG C of constant temperature keeps 1h to be completely dissolved to solid, then to clear solution
Middle addition 0.22g (1.0mmol) palladium acetate is as presoma, and 120 DEG C of agitating and heating 4h are to get Cabbeen-palladium solution.Gained is molten
Liquid is transferred in 25mL volumetric flask, is added DMF to corresponding scale, is obtained Cabbeen-palladium steeping liq that concentration is 0.001g/mL.
Using infusion process, Cabbeen-palladium maceration extract of metering is pipetted, and certain DMF is added and is mixed with maceration extract, then uniformly
By alumina support (specific surface area 420m2/ g) pour into maceration extract, and ultrasound.The Supported alumina of wetting is soaked in room temperature
Stain 12h, and the dry 12h at 110 DEG C, obtaining palladium load capacity is 0.04wt% with Cabbeen-palladium structure catalyst.
Embodiment 17
Referring to embodiment 4, difference is that the stirring condition by step (3) becomes: in 60 DEG C of stirring 4h, other conditions are the same as real
Example 4 is applied, it is 0.1wt% with Cabbeen-palladium structure catalyst that palladium load capacity, which is made,.
Embodiment 18
Referring to embodiment 4, difference is that the stirring condition by step (3) becomes: in 150 DEG C of stirring 2h, other conditions are same
Embodiment 4, it is 0.1wt% with Cabbeen-palladium structure catalyst that palladium load capacity, which is made,.
Embodiment 19
Referring to embodiment 4, difference is that the immersion condition by step (4) becomes: in room temperature immersion 8h, then at 130 DEG C
Lower dry 8h, for other conditions with embodiment 4, it is 0.1wt% with Cabbeen-palladium structure catalyst that palladium load capacity, which is made,.
Comparative example 1
Using palladium acetate as presoma, n,N-Dimethylformamide (DMF) is used as solvent, and preparation concentration is 0.001g/mL's
Palladium liquid.
Using infusion process, the palladium liquid of metering is pipetted, and certain DMF is added and is mixed with maceration extract, it then uniformly will oxidation
Alumina supporter (specific surface area 384m2/ g) pour into maceration extract, and ultrasound.The Supported alumina of wetting is small in room temperature immersion 12
When, and the dry 12h at 110 DEG C, obtain the alumina load palladium catalyst that palladium load capacity is 0.1wt%.
Catalyst obtained is subjected to catalyst activity and selective evaluation according to following method:
0.3g catalyst is placed in small-sized quartz tube reactor, quartz ampoule is placed in the heating furnace of controllable temperature, instead
Ying Qian is passed through pure H21h is restored at 100 DEG C;After reduction, (table 1) is reacted at a certain temperature.Reaction gas group becomes
(volume fraction): 0.33% acetylene, 0.66% hydrogen, 33% ethylene, surplus nitrogen.The flow velocity of reaction gas is 50mL/min, instead
Answering pressure is normal pressure.Reaction gas outlet connects gas-chromatography on-line checking, and the evaluation result of catalyst see the table below shown in 1.
1 alumina load ionic liquid of table-palladium catalyst selective hydrogenation of acetylene reaction evaluating result
Claims (10)
1. it is a kind of with Cabbeen-palladium structure catalyst, it is described including alumina support and the Cabbeen-palladium being supported on carrier
Catalyst passes through the preparation method included the following steps and is made:
(1) in a solvent by ion liquid dissolving, ionic liquid solution is obtained;The ionic liquid is with -3 methyl miaow of 1- ethyl
Azoles, -3 methylimidazole of 1- propyl, -3 methylimidazole of 1- butyl, -3 methylimidazole of 1- amyl or 1,3- bis- (2,6- diisopropyl benzenes)
Glyoxaline cation is cation, using chloride ion, bromide ion or iodide ion as anion;The solvent is selected from tetrahydrofuran, N, N-
One of dimethylformamide, dimethyl sulfoxide;
(2) powder potassium tert-butoxide or anhydrous sodium acetate are added into ionic liquid solution, 1-3h is stirred at 60-150 DEG C to be made admittedly
Body is completely dissolved to arrive Cabbeen solution;
(3) palladium presoma is proportionally added in Cabbeen solution, the palladium presoma is palladium acetate, palladium acetylacetonate or two
Chlorine diamino palladium, and 2-4h is stirred at 60-150 DEG C, it obtains containing Cabbeen-palladium solution;
(4) equably alumina support is poured into containing in Cabbeen-palladium solution, is totally submerged aluminium oxide by solution and sufficiently divides
It dissipates, the carrier soaked impregnates 8-14h at room temperature, and then the dry 8-14h at 110-130 DEG C, obtains with Cabbeen-palladium knot
The catalyst of structure.
2. having Cabbeen-palladium structure catalyst as described in claim 1, it is characterised in that: described that there is Cabbeen-palladium structure
Catalyst in palladium load capacity be 0.04-0.2wt%.
3. having Cabbeen-palladium structure catalyst as described in claim 1, it is characterised in that: the ionic liquid, the tert-butyl alcohol
The molar ratio of potassium or anhydrous sodium acetate, palladium presoma is 1:1-1.2:0.5-2.
4. having Cabbeen-palladium structure catalyst as described in claim 1, it is characterised in that: the specific surface of alumina support
Product is 58-420m2/g。
5. there is Cabbeen-palladium structure catalyst as described in one of Claims 1 to 4, it is characterised in that: the ionic liquid
Body is using chloride ion as anion;The solvent is N,N-dimethylformamide;The palladium presoma is palladium acetate.
6. having Cabbeen-palladium structure catalyst as claimed in claim 5, it is characterised in that: the ionic liquid is chlorine
Change -3 methylimidazole of 1- propyl.
7. there is Cabbeen-palladium structure catalyst as described in one of Claims 1 to 4 or 6, it is characterised in that: step (4)
In, if the aluminium oxide of addition can not be submerged containing Cabbeen-palladium solution, a certain amount of solvent is added, is completely submerged aluminium oxide;
After aluminium oxide is added, aluminium oxide is set to be uniformly dispersed in containing Cabbeen-palladium solution by ultrasonic treatment.
8. the application with Cabbeen-palladium structure catalyst in selective hydrogenation of acetylene reaction as described in claim 1,
Before, first catalyst is restored with hydrogen, reduction temperature is 60-150 DEG C, recovery time 1-3h.
9. application as claimed in claim 8, it is characterised in that: the condition of selective hydrogenation of acetylene reaction is: reaction temperature is
50-160 DEG C, reaction pressure 0.1-1MPa, air speed 4000-15000h-1。
10. application as claimed in claim 9, it is characterised in that: reaction temperature is 70-80 DEG C, and reaction pressure is normal pressure.
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