CN106669730B - A kind of catalyst and preparation method thereof for cis-butenedioic anhydride liquid-phase hydrogenatin - Google Patents
A kind of catalyst and preparation method thereof for cis-butenedioic anhydride liquid-phase hydrogenatin Download PDFInfo
- Publication number
- CN106669730B CN106669730B CN201510751453.2A CN201510751453A CN106669730B CN 106669730 B CN106669730 B CN 106669730B CN 201510751453 A CN201510751453 A CN 201510751453A CN 106669730 B CN106669730 B CN 106669730B
- Authority
- CN
- China
- Prior art keywords
- solution
- acid
- sncl
- citric acid
- catalyst
- 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.)
- Active
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 38
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 239000007791 liquid phase Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 96
- 239000000243 solution Substances 0.000 claims abstract description 50
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 40
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000000919 ceramic Substances 0.000 claims abstract description 32
- 238000007598 dipping method Methods 0.000 claims abstract description 25
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 21
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims abstract description 15
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims abstract description 15
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims abstract description 15
- 239000011734 sodium Substances 0.000 claims abstract description 14
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 14
- 230000001413 cellular effect Effects 0.000 claims abstract description 11
- 239000011259 mixed solution Substances 0.000 claims abstract description 11
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims abstract description 11
- 239000000758 substrate Substances 0.000 claims abstract description 11
- 238000005470 impregnation Methods 0.000 claims abstract description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 239000011148 porous material Substances 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 11
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 7
- 229910002666 PdCl2 Inorganic materials 0.000 claims description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- -1 hydrogen acid anhydride Chemical class 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 101150003085 Pdcl gene Proteins 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000007654 immersion Methods 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims description 2
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims 2
- 239000001119 stannous chloride Substances 0.000 claims 2
- 235000011150 stannous chloride Nutrition 0.000 claims 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- 239000002253 acid Substances 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 8
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 12
- 229940014800 succinic anhydride Drugs 0.000 description 12
- 239000000047 product Substances 0.000 description 7
- 238000011010 flushing procedure Methods 0.000 description 6
- 238000005984 hydrogenation reaction Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 6
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 244000248349 Citrus limon Species 0.000 description 4
- 235000005979 Citrus limon Nutrition 0.000 description 4
- 239000001384 succinic acid Substances 0.000 description 4
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 2
- 235000019799 monosodium phosphate Nutrition 0.000 description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- RRTCFFFUTAGOSG-UHFFFAOYSA-N benzene;phenol Chemical compound C1=CC=CC=C1.OC1=CC=CC=C1 RRTCFFFUTAGOSG-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 229910021478 group 5 element Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- BSIDXUHWUKTRQL-UHFFFAOYSA-N nickel palladium Chemical compound [Ni].[Pd] BSIDXUHWUKTRQL-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 238000007500 overflow downdraw method Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000013598 vector Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8966—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with germanium, tin or lead
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/651—50-500 nm
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/60—Two oxygen atoms, e.g. succinic anhydride
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention discloses a kind of preparation method of catalyst for cis-butenedioic anhydride liquid-phase hydrogenatin, includes the following steps: the SnCl of (1) using porous ceramics as carrier, using impregnation containing catechol2Solution is rinsed after dipping;(2) porous ceramics after being rinsed using step (1) dips palladium chloride solution, and the mixed solution of nickel sulfate, sodium dihydric hypophosphite and citric acid is impregnated after rinsing;(3) roast to the cellular ceramic substrate of the mixed solution of step (2) dipping nickel sulfate, sodium dihydric hypophosphite and citric acid the catalyst of obtained cis-butenedioic anhydride liquid-phase hydrogenatin.There is stronger active force between the catalyst activity component palladium and acid resistance carrier porous ceramics of this method preparation, active component palladium not easily runs off, and the stability of catalyst is largely increased.
Description
Technical field
The catalyst and preparation method thereof that the present invention relates to a kind of for cis-butenedioic anhydride liquid-phase hydrogenatin.
Background technique
With the breakthrough of butane oxidation maleic anhydride process, cis-butenedioic anhydride price declines, thus be hydrogenated by catalytic material of cis-butenedioic anhydride for
Succinic anhydride, succinic anhydride hydrolyzes again to be prepared succinic acid and attracts extensive attention, because succinic acid is a kind of common natural organic acids,
A kind of industrial important C4 compound, can be used as surfactant, detergent, green solvent, ion chelating agent, biology can
Degradable material, organic synthesis raw material, intermediate product or speciality chemical product be widely used in food, medicine, pesticide, dyestuff,
The fields such as fragrance, paint, plastics and material industry.And global succinic acid demand is continuously increased at present, so to maleic anhydride hydrogenation
The research that hydrolysis prepares succinic acid has practical significance.
Maleic anhydride hydrogenation technology is divided into two kinds at present: one is fusion method catalytic hydrogenation, another kind is solvent method liquid-phase hydrogenatin,
I.e. solvent dissolves cis-butenedioic anhydride, and catalyst system carries out liquid-phase hydrogenatin to cis-butenedioic anhydride solution.Solvent method liquid-phase hydrogenatin uses the Ith race and the VIIIth race
Element uses nickel for active component as hydrogenation active component in Chinese patent CN103769105A, and diatomite is urging for carrier
Agent, solvent method liquid-phase hydrogenatin obtain succinic anhydride product, but nickel, as active component, hydrogenation activity is not high, and catalyst
Active component nickel is lost serious.United States Patent (USP) US5952514 " technique for preparing succinic anhydride " uses the VIIIth race's element for catalysis
The active component of agent, and with the IVth race, group Ⅴ element alloy is mixed or formed to enhance the mechanical strength of catalyst.But
It is that the catalyst mentioned in this method contains one or more of Ni/Zr/Al/V/Si, catalyst service life can be generated
It influences, and has highly acid waste discharge in the subtractive process of succinic anhydride, have an adverse effect to environment.
In the prior art, precious metal palladium has good selectivity and higher conversion ratio maleic anhydride hydrogenation reaction.But
Maleic anhydride hydrogenation reaction system is acid system, and general acid nonfast carrier will lead to active component as carrier is lost together, resistance to
Acid vectors are such as: active carbon, ceramics are not because strong with palladium active force, the problem of also easily causing loss of active component.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of catalyst for cis-butenedioic anhydride liquid-phase hydrogenatin and its preparation side
Method.There is stronger active force, active component palladium is not easy between the catalyst activity component palladium and acid resistance carrier porous ceramics
It being lost, the stability of catalyst is largely increased, the second active component nickel is introduced,
It is prepared with the mode of alloying and further improves the stability of palladium.
A kind of preparation method of the catalyst for cis-butenedioic anhydride liquid-phase hydrogenatin, includes the following steps:
(1) SnCl using porous ceramics as carrier, using impregnation containing catechol2Solution, containing catechol
SnCl2The pH of solution is 1.5~6, preferably 2~4.5, further preferred 2.5~3;SnCl containing catechol2It is adjacent in solution
The mass concentration of benzenediol is 0.01~2%, preferably 0.01~0.5%, and the mass concentration of stannic chloride is 0.1~20g/L, preferably
0.5~10g/L is rinsed after dipping;
(2) porous ceramics after being rinsed using step (1) dips palladium chloride solution, and nickel sulfate, secondary phosphorus are impregnated after rinsing
The mixed solution of acid dihydride sodium and citric acid;
(3) to the cellular ceramic substrate of the mixed solution of step (2) dipping nickel sulfate, sodium dihydric hypophosphite and citric acid into
Row roasts the catalyst that cis-butenedioic anhydride liquid-phase hydrogenatin is made, and maturing temperature is 500~1500 DEG C, preferably 800~1200 DEG C.
In the method for the present invention, the SnCl containing catechol2Solution is the SnCl containing catechol2Aqueous solution.
In the method for the present invention, the pore volume of the cellular ceramic substrate is 0.2~1 cm3/ g, preferably 0.3~0.7
cm3/g;Porosity is 50~80%, and average pore size is 10~500nm, preferably 20~100nm.
In the method for the present invention, dipping is containing catechol after the cellular ceramic substrate preferably uses citric acid immersion treatment
SnCl2Solution, the mass concentration of citric acid are 1~20%, and soaking time is 3-7 h.After citric acid immersion treatment
Carrier can make the tin chloride solution of subsequent dipping evenly and rapidly form a film in the cell walls of porous ceramics, have reduction
Stannic chloride be evenly distributed in duct and can improve the dispersion degree of active component palladium in turn, further improve the work of catalyst
Property and stability.
In the method for the present invention, using HCl, sulfuric acid, nitric acid, perchloric acid, formic acid, oxalic acid, citric acid, succinic acid, carbonic acid, benzene
Phenol, phosphoric acid, phosphorous acid one or more adjust the SnCl containing catechol2Solution.
In the method for the present invention, HCl or citric acid are contained in palladium chloride solution, wherein PdCl2Mass content is 0.1~5g/
L, preferably 0.5~2g/L;HCl concentration is 1%~30%, preferably 1%~5%;Citric acid 0.5%~50%, preferably 1%~20%.
The method of the present invention, the SnCl containing catechol2The dipping and lessivation and PdCl of solution2The dipping process of solution
Alternately each SnCl2The dip time of solution is 5-15 seconds, and the elution time is 5-15 seconds, PdCl2The dip time of solution is
It 20-40 seconds, can repeat 1-20 times.Drying temperature is 80-120 DEG C after dipping.
In the method for the present invention, the quality of nickel sulfate is dense in the mixed aqueous solution of nickel sulfate, sodium dihydric hypophosphite and citric acid
Degree is 0.1~3g/L, and the mass concentration of sodium dihydric hypophosphite is 1-3g/L, and the mass concentration of citric acid is 2-4 g/L,
A kind of cis-butenedioic anhydride liquid phase hydrogenating catalyst prepared using the above method, the catalyst contain active group by weight
Divide palladium 0.1~3%, contains nickel 0.1~1%.
The application of above-mentioned cis-butenedioic anhydride liquid phase hydrogenating catalyst, reaction temperature are 90~150 DEG C, and reaction pressure is 0.5~3Mpa,
Volume space velocity is 0.1~1 when liquid, and hydrogen acid anhydride ratio is 50~200, preferably 100~130.
Compared with prior art, the catalyst of the method for the present invention preparation is used for cis-butenedioic anhydride liquid-phase hydrogenatin, forms nickel palladium appropriate
Alloy active component, active component palladium not easily run off, and the stability of catalyst long-term operation is significantly improved.
Specific embodiment
The process and effect of the method for the present invention are further illustrated below with reference to embodiment.But following embodiment is not constituted to this
The limitation of inventive method.Concentration is mass concentration to following embodiment unless otherwise specified.
Embodiment 1
Porous ceramic ball is weighed, the property of cellular ceramic substrate is as follows: pore volume 0.6cm3/g;Porosity is 70%,
Average pore size is 50nm.SnCl using above-mentioned porous ceramics as carrier, using impregnation containing catechol2Solution contains
The SnCl of catechol2The pH value of solution is 2.6, and pH value is adjusted using citric acid;SnCl containing catechol2It is adjacent in solution
The mass concentration of benzenediol is 0.1%, and the mass concentration of stannic chloride is 5g/L, is rinsed after dipping, dip time 10
Second, washing time is 10 seconds, impregnates and washs 1 time;Then palladium chloride solution is dipped using the porous ceramics after above-mentioned flushing.
Contain HCl in palladium chloride solution, wherein PdCl2Mass content is 0.1g/L, and HCl mass content is 5%, is repeated from SnCl2It is molten
For liquid to palladium chloride solution dipping process, dipping number is preferably 10 times, and nickel sulfate, sodium dihydric hypophosphite and lemon are impregnated after flushing
The mixed solution of acid, the mass concentration of nickel sulfate is 0.3g/L in mixed solution, and the mass concentration of sodium dihydric hypophosphite is 0. 2
G/L, the mass concentration of lemon acid are 0.3g/L.The catalyst that cis-butenedioic anhydride liquid-phase hydrogenatin is made finally is roasted, maturing temperature is
1200 DEG C, the mass content of palladium is 0.05% in terms of simple substance in catalyst, and the mass content of nickel is 0.01%.
The catalyst of above-mentioned preparation is packed into small fixed hydrogenator, 120 DEG C of reaction temperature, pressure 1.5Mpa,
Cis-butenedioic anhydride concentration 20wt% in reaction solution, remaining is gamma-butyrolacton, reacts liquid hourly space velocity (LHSV) 0.5h-1Under conditions of, hydrogen acid anhydride ratio 120v/
V, continuous 72h prepare succinic anhydride, conversion rate of maleic anhydride 80%, and succinic anhydride selectivity 80.7% does not detect palladium in the product.
Embodiment 2
Porous ceramic ball is weighed, the property of cellular ceramic substrate is as follows: pore volume 0.6cm3/g ;Porosity is 70%,
Average pore size is 50nm.SnCl using above-mentioned porous ceramics as carrier, using impregnation containing catechol2Solution contains
The SnCl of catechol2The pH value of solution is 2.6, and pH value is adjusted using citric acid;SnCl containing catechol2Adjacent benzene in solution
The mass concentration of diphenol is 0.1%, and the mass concentration of stannic chloride is 5g/L, is rinsed after dipping, dip time 10
Second, washing time is 10 seconds, impregnates and washs 1 time;Then palladium chloride solution is dipped using the porous ceramics after above-mentioned flushing.
Contain HCl in palladium chloride solution, wherein PdCl2Mass content is 0.1g/L, and HCl mass content is 5%, is repeated from SnCl2It is molten
For liquid to palladium chloride solution dipping process, dipping number is preferably 10 times, is rinsed after dipping, and nickel sulfate, secondary is impregnated after flushing
The mixed solution of sodium dihydrogen phosphate and citric acid, the mass concentration of nickel sulfate is 0.3 g/L, hypophosphorous acid dihydro in mixed solution
The mass concentration of sodium is 0.2g/L, and the mass concentration of citric acid is 0.3g/L.It finally roasts and urging for cis-butenedioic anhydride liquid-phase hydrogenatin is made
Agent, maturing temperature are 1200 DEG C, and the mass content of palladium is 0.05% in terms of simple substance in catalyst, and the mass content of nickel is
0.01%。
Above-mentioned catalyst is packed into small fixed hydrogenator, 120 DEG C of reaction temperature, pressure 2.0Mpa, is reacted molten
Cis-butenedioic anhydride concentration 5wt% in liquid, remaining is gamma-butyrolacton, reacts liquid hourly space velocity (LHSV) 0.5h-1Under conditions of, hydrogen acid anhydride ratio 120v/v, continuously
72h prepares succinic anhydride, conversion rate of maleic anhydride 91%, succinic anhydride selectivity 95.5%, and does not detect palladium in the product.
Embodiment 3
Porous ceramic ball is weighed, the property of cellular ceramic substrate is as follows: pore volume 0.6cm3/g ;Porosity is 70%,
Average pore size is 50nm.SnCl using above-mentioned porous ceramics as carrier, using impregnation containing catechol2Solution contains
The SnCl of catechol2The pH value of solution is 2.6, and pH value is adjusted using citric acid;SnCl containing catechol2Adjacent benzene in solution
The mass concentration of diphenol is 0.1%, and the mass concentration of stannic chloride is 5g/L, is rinsed after dipping, dip time 10
Second, washing time is 10 seconds, impregnates and washs 1 time;Then palladium chloride solution is dipped using the porous ceramics after above-mentioned flushing.
Contain HCl in palladium chloride solution, wherein PdCl2Mass content is 0.5 g/L, and HCl mass content is 5%, is repeated from SnCl2It is molten
For liquid to palladium chloride solution dipping process, dipping number is preferably 10 times, is rinsed after dipping, and nickel sulfate, secondary is impregnated after flushing
The mixed solution of sodium dihydrogen phosphate and citric acid, 0.3 g/L, the mass concentration of sodium dihydric hypophosphite are 0.2g/L, citric acid
Mass concentration is 0.3g/L.The catalyst that cis-butenedioic anhydride liquid-phase hydrogenatin is made finally is roasted, maturing temperature is 1200 DEG C, catalyst
In in terms of simple substance the mass content of palladium be 0.3%, the mass content of nickel is 0.05%.
Above-mentioned catalyst is packed into small fixed hydrogenator, 120 DEG C of reaction temperature, pressure 2.0Mpa, is reacted molten
Cis-butenedioic anhydride concentration 5wt% in liquid, remaining is gamma-butyrolacton, reacts liquid hourly space velocity (LHSV) 0.5h-1Under conditions of, hydrogen acid anhydride ratio 120v/v, continuously
Add hydrogen 500h activity without decline, conversion rate of maleic anhydride 93.8%, succinic anhydride selectivity 96.5%, and does not detect in the product
Palladium.
Embodiment 4
It is that, using the porous ceramic ball after lemon acid soak, citric acid concentration is with the different place of embodiment 1
20%, soaking time 5h.The quality of palladium simple substance in catalyst is made with embodiment 1 in remaining preparation process and evaluation procedure
Content is 0.3% continuously hydrogen adding 500h activity without decline, conversion rate of maleic anhydride 90%, succinic anhydride selectivity 92.5%, and in product
In do not detect palladium.
Embodiment 5
It is with the different place of embodiment 2 using the porous ceramic ball after lemon acid soak, citric acid concentration 20%
, soaking time 5h.Remaining preparation process and evaluation procedure are the same as embodiment 1.The mass content of palladium simple substance in catalyst is made
It is 0.5%.Continuously hydrogen adding 500h activity is without decline, conversion rate of maleic anhydride > 98.5%, succinic anhydride selectivity > 99.8%, and
Palladium is not detected in product.
Claims (13)
1. a kind of preparation method of the catalyst for cis-butenedioic anhydride liquid-phase hydrogenatin, characterized by the following steps:
(1) SnCl using porous ceramics as carrier, using impregnation containing catechol2Solution, the SnCl containing catechol2
The pH of solution is 1.5~6;SnCl containing catechol2The mass concentration of catechol is 0.01~2% in solution, stannous chloride
Mass concentration be 0.1~20g/L, be rinsed after dipping;
(2) porous ceramics after being rinsed using step (1) dips palladium chloride solution, and nickel sulfate, hypophosphorous acid two are impregnated after rinsing
The mixed solution of hydrogen sodium and citric acid;
(3) cellular ceramic substrate of the mixed solution of step (2) dipping nickel sulfate, sodium dihydric hypophosphite and citric acid is roasted
Fire cis-butenedioic anhydride liquid-phase hydrogenatin catalyst, maturing temperature be 500~1500 DEG C.
2. according to the method described in claim 1, it is characterized by: the SnCl containing catechol2The pH of solution is 2~4.5;Contain
The SnCl of catechol2The mass concentration of catechol is 0.01~0.5% in solution, the mass concentration of stannous chloride is 0.5~
10g/L。
3. according to the method described in claim 1, it is characterized by: the SnCl containing catechol2Solution is containing adjacent benzene two
The SnCl of phenol2Aqueous solution.
4. according to the method described in claim 1, it is characterized by: the pore volume of the cellular ceramic substrate is 0.2~1
cm3/g;Porosity is 50~80%, and average pore size is 10~500nm.
5. according to the method described in claim 4, it is characterized by: the pore volume of the cellular ceramic substrate is 0.3~0.7
cm3/g;Average pore size is 20~100nm.
6. according to the method described in claim 1, it is characterized by: the cellular ceramic substrate uses citric acid immersion treatment
The SnCl containing catechol is impregnated afterwards2Solution, the mass concentration of citric acid are 1~20%, and soaking time is 3-7 h.
7. according to the method described in claim 1, it is characterized by: using HCl, sulfuric acid, nitric acid, perchloric acid, formic acid, oxalic acid,
One or more of citric acid, succinic acid, carbonic acid, phenol, phosphoric acid, phosphorous acid adjust the SnCl containing catechol2Solution.
8. according to the method described in claim 1, it is characterized by: containing HCl or citric acid, wherein PdCl in palladium chloride solution2
Mass content is 0.1~5g/L;HCl mass content is 1%~30%;Citric acid 0.5%~50%.
9. according to the method described in claim 1, it is characterized by: containing HCl or citric acid, wherein PdCl in palladium chloride solution2
Mass content is 0.5~2g/L;HCl mass content is 1%~5%;Citric acid 1%~20%.
10. according to the method described in claim 1, it is characterized by: the SnCl containing catechol2The dipping of solution and flushed
Journey and PdCl2The alternately each SnCl of the dipping process of solution2The dip time of solution is 5-15 seconds, washing time 5-15
Second, PdCl2The dip time of solution is 20-40 seconds, is repeated 1-20 times, and drying temperature is 80-120 DEG C after dipping.
11. according to the method described in claim 1, it is characterized by: the mixing of nickel sulfate, sodium dihydric hypophosphite and citric acid is molten
The mass concentration of nickel sulfate is 0.1~3g/L in liquid, and the mass concentration of sodium dihydric hypophosphite is 1-3g/L, and the quality of citric acid is dense
Degree is 2-4 g/L.
12. a kind of catalyst prepared using claim 1 to 11 either method, it is characterised in that: the catalyst is by weight
Meter contains active component palladium 0.1~3%, contains nickel 0.1~1%.
13. application of the catalyst described in claim 12 in cis-butenedioic anhydride liquid-phase hydrogenatin, it is characterised in that: reaction temperature be 90~
150 DEG C, reaction pressure is 0.5~3Mpa, and volume space velocity is 0.1~1 when liquid, and hydrogen acid anhydride ratio is 50~200 v/v.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201510751453.2A CN106669730B (en) | 2015-11-09 | 2015-11-09 | A kind of catalyst and preparation method thereof for cis-butenedioic anhydride liquid-phase hydrogenatin |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201510751453.2A CN106669730B (en) | 2015-11-09 | 2015-11-09 | A kind of catalyst and preparation method thereof for cis-butenedioic anhydride liquid-phase hydrogenatin |
Publications (2)
Publication Number | Publication Date |
---|---|
CN106669730A CN106669730A (en) | 2017-05-17 |
CN106669730B true CN106669730B (en) | 2019-03-19 |
Family
ID=58862875
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201510751453.2A Active CN106669730B (en) | 2015-11-09 | 2015-11-09 | A kind of catalyst and preparation method thereof for cis-butenedioic anhydride liquid-phase hydrogenatin |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN106669730B (en) |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102311332A (en) * | 2010-07-07 | 2012-01-11 | 中国石油化工股份有限公司 | Method for producing succinic acid |
CN103769117A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Catalyst for hydrogenating cis-butenedioic anhydride to prepare butanedioic anhydride and its preparation method and application |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20050049434A1 (en) * | 2003-08-28 | 2005-03-03 | Tustin Gerald Charles | Fluidizable carbon catalysts |
-
2015
- 2015-11-09 CN CN201510751453.2A patent/CN106669730B/en active Active
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102311332A (en) * | 2010-07-07 | 2012-01-11 | 中国石油化工股份有限公司 | Method for producing succinic acid |
CN103769117A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Catalyst for hydrogenating cis-butenedioic anhydride to prepare butanedioic anhydride and its preparation method and application |
Also Published As
Publication number | Publication date |
---|---|
CN106669730A (en) | 2017-05-17 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN103785400B (en) | A kind of preparation method of high activity residuum hydrogenating and metal-eliminating catalyst | |
CN103966473A (en) | Surface Modified Metallic Foam Body, Process For Its Production And Use Thereof | |
CN104151129B (en) | The method of selective hydrogenation of alpha-methyl-styrene | |
CN100451166C (en) | Chemical plating activating process and metal depositing process therewith | |
CN102441374A (en) | Selective hydrogenation catalyst and its preparation method and application | |
CN109833883A (en) | A kind of high activity bimetallic load combustion catalyst and preparation method thereof | |
CN102614870B (en) | Vinylacetylene hydrogenation catalyst and preparation method thereof | |
CN102626619A (en) | Preparation method of palladium carbon catalyst | |
CN103480370A (en) | Preparation method of carbon supported Pd-Pt metallic catalyst for catalytic hydrogenation | |
CN104178752A (en) | Activation method used before chemical plating of palladium or palladium alloy film | |
CN107159308A (en) | A kind of Ni-based molecular sieve catalyst and preparation method thereof | |
CN108250044A (en) | A kind of preparation method and application of alkyl cyclohexanol | |
CN106669730B (en) | A kind of catalyst and preparation method thereof for cis-butenedioic anhydride liquid-phase hydrogenatin | |
CN106669745B (en) | A kind of maleic anhydride hydrogenation prepares catalyst of succinic anhydride and preparation method thereof | |
CN102011108A (en) | Chemical plating method for preparing ultrathin palladium film with high specific surface area | |
CN109833890A (en) | A kind of residual oil hydrocatalyst and its preparation | |
CN102626621A (en) | Hydrogenation catalyst using cellular titanium dioxide as carrier and preparation method thereof | |
CN100451044C (en) | Catalyst for preparing C5 hydrogenated petroleum resin, and its preparing method | |
CN102943255B (en) | Preparation process of nickel-coated silicon carbide powder for surface enhancement of impression of hot forging mold | |
CN102895970A (en) | Method for preparing Pd/C catalyst by using organic aerogel supported Pd compound and Pd/C catalyst | |
CN102626620A (en) | Preparation method of palladium carbon catalyst with controllable load depth | |
CN109433214A (en) | A kind of porous catalysts supported on carbon of Ni/Zn and its application in phenyl ring catalytic hydrogenation | |
CN106140288B (en) | A kind of dimethyl ether directly prepares the catalyst and its preparation method and application of hexamethylbenzene | |
CN102350361A (en) | Nickel-based structured catalyst for synthesizing m-phenylenediamine through hydrogenation of m-dinitrobenzene and its preparation method | |
CN104962774A (en) | Super-structure Pd-Cu alloy and preparation method thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |