CN111072487B - Method for preparing hexamethylenediamine based on cyclohexene - Google Patents
Method for preparing hexamethylenediamine based on cyclohexene Download PDFInfo
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- CN111072487B CN111072487B CN201911295990.5A CN201911295990A CN111072487B CN 111072487 B CN111072487 B CN 111072487B CN 201911295990 A CN201911295990 A CN 201911295990A CN 111072487 B CN111072487 B CN 111072487B
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- cyclohexene
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- hydrotalcite
- based catalyst
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- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 title claims abstract description 90
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 238000000034 method Methods 0.000 title claims abstract description 32
- 239000003054 catalyst Substances 0.000 claims abstract description 87
- 238000006243 chemical reaction Methods 0.000 claims abstract description 46
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims abstract description 40
- 229960001545 hydrotalcite Drugs 0.000 claims abstract description 40
- 229910001701 hydrotalcite Inorganic materials 0.000 claims abstract description 40
- UMHJEEQLYBKSAN-UHFFFAOYSA-N Adipaldehyde Chemical compound O=CCCCCC=O UMHJEEQLYBKSAN-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000007789 gas Substances 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 15
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000001257 hydrogen Substances 0.000 claims abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 5
- 229910052751 metal Inorganic materials 0.000 claims description 33
- 239000002184 metal Substances 0.000 claims description 33
- 239000011259 mixed solution Substances 0.000 claims description 33
- 150000001768 cations Chemical class 0.000 claims description 25
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 20
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 19
- 238000002360 preparation method Methods 0.000 claims description 16
- 229910052723 transition metal Inorganic materials 0.000 claims description 7
- 150000003624 transition metals Chemical class 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- 239000012752 auxiliary agent Substances 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 6
- 238000011068 loading method Methods 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- WRQNANDWMGAFTP-UHFFFAOYSA-N Methylacetoacetic acid Chemical compound COC(=O)CC(C)=O WRQNANDWMGAFTP-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- FSJSYDFBTIVUFD-SUKNRPLKSA-N (z)-4-hydroxypent-3-en-2-one;oxovanadium Chemical compound [V]=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FSJSYDFBTIVUFD-SUKNRPLKSA-N 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000012266 salt solution Substances 0.000 claims description 3
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims description 2
- 239000003570 air Substances 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- CWKLZLBVOJRSOM-UHFFFAOYSA-N methyl pyruvate Chemical group COC(=O)C(C)=O CWKLZLBVOJRSOM-UHFFFAOYSA-N 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- RYSXWUYLAWPLES-MTOQALJVSA-N (Z)-4-hydroxypent-3-en-2-one titanium Chemical compound [Ti].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O RYSXWUYLAWPLES-MTOQALJVSA-N 0.000 claims 1
- IAWVHZJZHDSEOC-UHFFFAOYSA-M 3,3-dimethyl-2-oxobutanoate Chemical compound CC(C)(C)C(=O)C([O-])=O IAWVHZJZHDSEOC-UHFFFAOYSA-M 0.000 claims 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims 1
- IZJWUPAJEFJGHC-UHFFFAOYSA-N methyl 3-fluoro-2-oxopropanoate Chemical compound COC(=O)C(=O)CF IZJWUPAJEFJGHC-UHFFFAOYSA-N 0.000 claims 1
- 229910052750 molybdenum Inorganic materials 0.000 claims 1
- 239000011733 molybdenum Substances 0.000 claims 1
- SYECJBOWSGTPLU-UHFFFAOYSA-N hexane-1,1-diamine Chemical compound CCCCCC(N)N SYECJBOWSGTPLU-UHFFFAOYSA-N 0.000 abstract description 14
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 abstract description 10
- 238000006268 reductive amination reaction Methods 0.000 abstract description 8
- 230000001590 oxidative effect Effects 0.000 abstract description 4
- 239000002638 heterogeneous catalyst Substances 0.000 abstract description 3
- 239000007800 oxidant agent Substances 0.000 abstract description 3
- 231100000331 toxic Toxicity 0.000 abstract description 3
- 230000002588 toxic effect Effects 0.000 abstract description 3
- 150000002736 metal compounds Chemical class 0.000 abstract description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 58
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- 239000002243 precursor Substances 0.000 description 14
- 229910002651 NO3 Inorganic materials 0.000 description 12
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 12
- 230000032683 aging Effects 0.000 description 10
- 239000006185 dispersion Substances 0.000 description 10
- 229910003275 NiMgAl Inorganic materials 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 238000001816 cooling Methods 0.000 description 7
- 239000012153 distilled water Substances 0.000 description 7
- 230000007935 neutral effect Effects 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 239000000725 suspension Substances 0.000 description 7
- 238000005406 washing Methods 0.000 description 6
- 229920002302 Nylon 6,6 Polymers 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- JBDIMNRIQHSXQD-UHFFFAOYSA-N [C].C(CCCCC=O)=O Chemical compound [C].C(CCCCC=O)=O JBDIMNRIQHSXQD-UHFFFAOYSA-N 0.000 description 3
- 238000005576 amination reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- NPEIGRBGMUJNFE-UHFFFAOYSA-N 1-aminohexan-1-ol Chemical compound CCCCCC(N)O NPEIGRBGMUJNFE-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- NZOHLEDRKVIKHS-UHFFFAOYSA-N NCCCCCCN.[C] Chemical compound NCCCCCCN.[C] NZOHLEDRKVIKHS-UHFFFAOYSA-N 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical compound [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000010813 internal standard method Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- ADVORQMAWLEPOI-XHTSQIMGSA-N (e)-4-hydroxypent-3-en-2-one;oxotitanium Chemical compound [Ti]=O.C\C(O)=C/C(C)=O.C\C(O)=C/C(C)=O ADVORQMAWLEPOI-XHTSQIMGSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical class [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- AJCADVIJLINZNT-UHFFFAOYSA-N C(C)O.C(CCCCC#N)#N Chemical compound C(C)O.C(CCCCC#N)#N AJCADVIJLINZNT-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- -1 alkaline earth metal salt Chemical class 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- XGLLQDIWQRQROJ-UHFFFAOYSA-N methyl 3,3,3-trifluoro-2-oxopropanoate Chemical compound COC(=O)C(=O)C(F)(F)F XGLLQDIWQRQROJ-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229940094933 n-dodecane Drugs 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(II) nitrate Inorganic materials [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 201000010041 presbyopia Diseases 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/24—Preparation of compounds containing amino groups bound to a carbon skeleton by reductive alkylation of ammonia, amines or compounds having groups reducible to amino groups, with carbonyl compounds
- C07C209/26—Preparation of compounds containing amino groups bound to a carbon skeleton by reductive alkylation of ammonia, amines or compounds having groups reducible to amino groups, with carbonyl compounds by reduction with hydrogen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/34—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with ozone; by hydrolysis of ozonides
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The application discloses a method for preparing hexamethylene diamine based on cyclohexene, which comprises the following steps: respectively injecting mixed liquor and mixed gas containing ozone into a microchannel reactor, and carrying out oxidation reaction under reaction conditions to obtain adipic dialdehyde, wherein the mixed liquor contains cyclohexene and a metal compound catalyst; reacting the raw material containing the hexanedial in the presence of ammonia gas, hydrogen and a Ni-based catalyst to generate hexanediamine; wherein the Ni-based catalyst consists of Ni2+And (3) preparing the hydrotalcite. The hexamethylene diamine is prepared by oxidizing and aminating cyclohexene serving as a raw material, so that a highly toxic raw material adiponitrile is avoided, ozone serving as an oxidant is adopted, the adipic dialdehyde can be prepared by a heterogeneous catalyst at high selectivity, a Ni-based catalyst is further adopted to catalyze the adiponitrile to prepare the hexamethylene diamine by reductive amination, the highly toxic raw material adiponitrile is avoided, and the route is clean and environment-friendly.
Description
Technical Field
The application relates to a method for preparing hexamethylene diamine based on cyclohexene, and belongs to the field of chemical engineering.
Background
Hexamethylenediamine is an important organic chemical raw material, and can be used for preparing polyhexamethylene adipamide, also called polyamide 66(PA66) or nylon 66, by a polycondensation reaction with adipic acid. Nylon 66 can be used for injection molding, extrusion, blow molding, spray coating, cast molding, machining, welding, bonding. About 90% of the world's annual production of hexamethylenediamine is used in the production of nylon 66. The production technology of hexamethylenediamine mainly comprises an adiponitrile method, a hexanediol method and a caprolactam method. Currently, hexamethylenediamine is almost exclusively prepared by hydrogenation of adiponitrile, which is produced by processes such as adipic acid catalytic amination, acrylonitrile electrolytic dimerization and butadiene.
CN108084035A discloses a method for preparing hexanediamine by directly hydrogenating adiponitrile under the alkali-free condition, wherein an alkaline earth metal oxide or rare earth metal oxide modified aluminum trioxide supported metal nickel catalyst prepared by a coprecipitation method is used for preparing hexanediamine by hydrogenating an adiponitrile ethanol solution with a certain concentration. CN106807377A discloses a method for synthesizing hexamethylenediamine under the condition of hydrogenation by using a catalyst which takes one or more of Ni or Co main active components Fe, Cu, Ru, Re, K, Zn, B and other metals or oxides as an auxiliary agent to catalyze the ammoniation reaction of hexanediol or aminohexanol or hexanediol/aminohexanol mixture. CN104262168B discloses a method for preparing hexamethylenediamine by aminating hexanedial with nickel-based hydrogenation catalyst loaded on silica carrier.
From the literature and the technology which are available at present, the raw material adiponitrile in the industrialized adiponitrile hydrogenation preparation route of the hexamethylenediamine is high in toxicity, dependent on import and high in price. The development of a new green hexamethylenediamine preparation process is of great significance. Therefore, the development of a catalyst with good catalyst activity and target product selectivity is the key for realizing a green new process of the hexamethylene diamine.
Disclosure of Invention
According to one aspect of the application, the cyclohexene-based method for preparing the hexanediamine is provided, the cyclohexene is used as a raw material, the ozone is used as an oxidant, the heterogeneous catalyst can be used for preparing the hexanediamine in a high-selectivity manner, the Ni-based catalyst is further used for catalyzing the hexanediamine to prepare the hexanediamine through reductive amination, the use of a highly toxic raw material adiponitrile is avoided, and the route is clean and environment-friendly.
The cyclohexene-based method for preparing hexamethylene diamine comprises the following steps:
(a) respectively injecting mixed liquor and mixed gas containing ozone into a microchannel reactor, and carrying out oxidation reaction under reaction conditions to obtain adipic dialdehyde, wherein the mixed liquor contains cyclohexene and a metal compound catalyst;
(b) reacting the raw material containing the hexanedial in the presence of ammonia gas, hydrogen and a Ni-based catalyst to generate hexanediamine; wherein the Ni-based catalyst consists of Ni2+And (3) preparing the hydrotalcite. Specifically, the Ni-containing alloy of the present invention2+The hydrotalcite is that divalent metal ions forming a layered structure of the hydrotalcite contain Ni2+；
The reaction conditions in step (a) include:
the hydraulic diameter of the microchannel reactor is 20-2000 um, and the effective contact time of the mixed liquid and the mixed gas in the microchannel reactor is 0.1-60 s. The reaction temperature is-70-50 ℃, and preferably-20 ℃;
the reaction pressure is 0.1-1.0 MPa;
the molar ratio of the ozone to the cyclohexene is 0.50-3.0.
Alternatively, the upper limit of the reaction temperature may be selected from 70 ℃, 50 ℃, 40 ℃, 30 ℃, 20 ℃, 15 ℃, 10 ℃, 5 ℃, 0 ℃, -5 ℃, -15 ℃, -10 ℃ or-20 ℃, and the lower limit may be selected from 40 ℃, 30 ℃, 20 ℃, 15 ℃, 10 ℃, 5 ℃, 0 ℃, -5 ℃, -10 ℃, -15 ℃, -20 ℃ or-30 ℃.
Optionally, the mixture further comprises:
at least one of oxygen, air, and inert gas;
the concentration of ozone in the mixed gas is 10-140 mg/L.
Optionally, the upper limit of the concentration of ozone in the mixed gas is selected from 140mg/L, 130mg/L, 120mg/L, 110mg/L, 100mg/L, 90mg/L, 80mg/L, 70mg/L, 60mg/L, 50mg/L, 40mg/L, 30mg/L or 20mg/L, and the lower limit is selected from 130mg/L, 120mg/L, 110mg/L, 100mg/L, 90mg/L, 80mg/L, 70mg/L, 60mg/L, 50mg/L, 40mg/L, 30mg/L, 20mg/L or 10 mg/L;
the transition metal complex catalyst is at least one of vanadyl acetylacetonate, molybdyl acetylacetonate and titanyl acetylacetonate;
the mass ratio of the transition metal complex catalyst to the cyclohexene is (0.05-0.3): 1;
preferably, the mass ratio of the transition metal complex catalyst to the cyclohexene is (0.10-0.20): 1.
optionally, the mixed solution further contains an ester auxiliary agent; the ester auxiliary agent is selected from at least one of methyl pyruvate, methyl trifluoropyruvate, methyl acetylacetonate and methyl acetoacetate; the molar ratio of the ester auxiliary agent to the cyclohexene is (0.1-0.5): 1, preferably (0.1-0.3) 1; the mixed solution also contains an organic solvent;
the organic solvent is at least one of acetone, acetonitrile and ethanol.
Optionally, the reaction conditions in step (b) include:
the reaction temperature is 80-200 ℃, and preferably 80-150 ℃;
the reaction pressure is 1-20 Mpa, preferably 5-10 Mpa.
The mol ratio of ammonia to adipaldehyde is 5-60: 1, the molar ratio of hydrogen to adipaldehyde is 5-60: 1.
optionally, the divalent metal cations of the hydrotalcite in step (b) further comprise Mg2+、Co2+、Zn2+Or Cu2+At least one of;
the trivalent metal cation of the hydrotalcite is selected from Al3+、Cr3+、Fe3+Or Sc3+At least one of; the mass content of Ni in the Ni-based catalyst is 5-50%;
the molar ratio of divalent metal cations to trivalent metal cations of the hydrotalcite is 1.0-4.0: 1, wherein Ni2+The molar ratio of the metal ions to other divalent metal cations is 0.1-100: 1.
alternatively, Ni2+The upper limit of the molar ratio to the other divalent metal cation may be selected from 100:1, 10:1, 9:1, 8:1, 7:1, 6:1, 5:1, 4:1, 3:1, 2:1, 1:1 or 0.5:1, and the lower limit may be selected from 10:1, 9:1, 8:1, 7:1, 6:1, 5:1, 4:1, 3:1, 2:1, 1:1, 0.5:1 or 0.1: 1.
Optionally, the Ni-based catalyst is an alkaline earth metal modified Ni-based catalyst;
the alkaline earth metal comprises at least one of Mg, Ca, Sr and Ba;
the mass loading of the alkaline earth metal is 1.0-5.0%.
In the examples of the present invention, the alkali metal mass loading was based on the total amount of the catalyst. Alternatively, the alkali metal may be supported at an upper limit selected from 5.0%, 4.0%, 3.0% or 2.0% and at a lower limit selected from 4.0%, 3.0%, 2.0% or 1.0% by mass.
Alternatively, the alkaline earth metal-modified Ni-based catalyst is obtained by:
adding a raw material containing the Ni-based catalyst into a salt solution containing alkaline earth metal, soaking in the same volume, and roasting to obtain the alkaline earth metal modified Ni-based catalyst.
Alternatively, the Ni-based catalyst consists of Ni2+The hydrotalcite is obtained by roasting.
Optionally, the preparation method of the alkaline earth metal modified Ni-based catalyst specifically includes:
(1) coprecipitating the mixed solution I containing metal cations and the mixed solution II containing a precipitator, and aging to obtain Ni-based hydrotalcite (containing Ni)2+Hydrotalcite) to obtain a Ni-based catalyst; wherein the metal cation comprises a divalent metal cation comprising Ni and a trivalent metal cation2+。
(2) Adding a raw material containing the Ni-based catalyst into a salt solution containing alkaline earth metal, soaking in the same volume, and roasting to obtain the alkaline earth metal modified Ni-based catalyst.
Optionally, the divalent metal cation further comprises Mg2+、Co2+、Zn2+Or Cu2+At least one of;
the trivalent metal cation is selected from Al3+、Cr3+、Fe3+Or Sc3+At least one of; the molar ratio of divalent metal cations to trivalent metal cations of the hydrotalcite is 2.5-3.5: 1, and Ni2+The molar ratio of the metal ions to other divalent metal cations is 0.1-100: 1.
optionally, the reaction conditions of the coprecipitation of step (1) include:
the temperature is 60-70 ℃;
the pH value is 8-12.
Optionally, the metal cation is from at least one of nitrate, sulfate, acetate, chloride of the metal; the precipitant is Na2CO3At least one of NaOH and ammonia water.
Optionally, the aging conditions include:
the aging temperature is 60-70 ℃;
the time for presbyopia is 36-96 h.
Alternatively, the firing conditions after the Ni-based hydrotalcite is prepared include:
the temperature is 400-600 ℃;
the roasting time is 3-5 h.
Optionally, the reactor is selected from one of a fixed bed reactor, a trickle bed or a tank reactor.
The beneficial effects that this application can produce include:
compared with the prior art, the technology adopts cyclohexene as a raw material, and the hexamethylene diamine is prepared through oxidation and amination, so that the use of a virulent raw material adiponitrile is avoided;
ozone is used as an oxidant, a heterogeneous catalyst can be used for preparing hexanedial in a high-selectivity manner, and a Ni-based hydrotalcite catalyst is further used for catalyzing hexanedial to prepare hexanediamine through reductive amination, so that the route is clean and environment-friendly;
the high-dispersion Ni-based catalyst is prepared by using a hydrotalcite precursor, so that the dispersion degree of Ni is effectively improved, the acidity and alkalinity of the catalyst are adjusted through alkaline earth metal modification, the prepared catalyst has the characteristics of metal catalysis and alkaline catalysis, and the adsorption on amine can be reduced when the catalyst is applied to the reductive amination reaction of hexanedial, so that the side reaction is reduced, and good activity and selectivity are shown;
the catalyst provided by the invention has the advantages of simple preparation method, convenience in operation, low cost, reusability and potential economic benefit.
Detailed Description
The present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.
The water conservancy diameter of the micro-channel reactor used in the embodiment of the invention is 500 microns, and the gas-liquid contact time is 10 seconds.
The present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.
The raw materials in the examples of the present invention were all purchased from commercial sources unless otherwise specified.
The analytical methods and conversion, selectivity in the examples were calculated as follows:
the analytical methods and conversion, selectivity in the examples were calculated as follows:
automated analysis was performed using an Agilent7890 gas chromatograph with an autosampler. Analysis of cyclohexene oxidation reaction products: adding n-dodecane into the reaction solution after the reaction as an internal standard, and quantifying by adopting an internal standard method.
In some embodiments of the invention, both conversion and selectivity are calculated based on carbon moles:
cyclohexene conversion (mol) ═ [ (cyclohexene amount in feed) - (cyclohexene amount in discharge) ]/(cyclohexene amount in feed) × 100%
Adipaldehyde selectivity (mol) — (amount of adipaldehyde in the discharge) ÷ (amount of cyclohexene converted) × 100%
Analysis of the amination product of adipaldehyde: analysis was performed using an Agilent7890 gas chromatograph with an autosampler. After the reaction is finished, adding n-octylamine into the reaction solution as an internal standard, and carrying out quantitative analysis by an internal standard method.
In some embodiments of the invention, both conversion and selectivity are calculated based on carbon moles:
conversion of adipaldehyde [ (adipaldehyde carbon mole number in feed) - (adipaldehyde carbon mole number in discharge) ]/(adipaldehyde carbon mole number in feed) × 100%
Hexamethylenediamine selectivity (the mole number of hexamethylenediamine carbon in the discharged material) ÷ (the total mole number of all carbon-containing products in the discharged material) × 100%
The hexamethylenediamine yield (moles of hexamethylenediamine carbon in the output)/moles of hexamethylenedialdehyde carbon converted) 100%.
Example 1' Oxidation of cyclohexene to adipaldehyde in a Microchannel reactor
Mixing 50g of cyclohexene and 116g of acetone to prepare a cyclohexene solution with the mass concentration of 30%, adding 7.89g of vanadyl acetylacetonate into the cyclohexene solution, and uniformly mixing by ultrasonic oscillation to obtain a mixed solution;
injecting the mixed solution into a microchannel reactor by using a pump, wherein the flow rate of the mixed solution is 10g/min, injecting the mixed gas into the microchannel reactor through a mass flow meter, and controlling the flow rate of the mixed gas to be 15.1L/min, wherein the mixed gas consists of oxygen and ozone, and the concentration of the ozone is 100 mg/L;
the reaction temperature in the microchannel reactor is 10 ℃, the reaction pressure is 0.10MPa, the materials are collected after 10min of reaction, and gas chromatography is adopted for analysis.
Example 2 '-11' Oxidation of cyclohexene to adipaldehyde in a Microchannel reactor
The reaction was carried out by changing the pressure, solvent, catalyst and reaction temperature of the reaction by the procedure described in example 1', and the specific reaction conditions and results are shown in Table 1.
TABLE 1 reaction conditions and results tabulated for cyclohexene oxidation to hexanedial in microchannel reactor
As can be seen from table 1, the preparation process provided by the present application generally has a high selectivity of adipaldehyde, which can reach 53.8% or more, and can reach 91.2% at the highest, and the conversion rate of cyclohexene can reach 35.2% or more, and can reach 100% at the highest.
Preparation of Ni-based catalyst: the ion ratios in the following examples are molar ratios unless otherwise specified.
EXAMPLE 1 preparation of NiMgAl-01 catalyst Using hydrotalcite as precursorAgent (Ni)2++Mg2+)：Al3+The ratio of (A) to (B) is 3:1, Ni2+：Mg2+The ratio of (A) to (B) is 0.1.
9.52gNi(NO3)2·6H2O，46.89gAl(NO3)3·9H2O and 83.92gMg (NO)3)2·6H2Completely dissolving O in 500ml of water to obtain a mixed solution I; 26.5g Na were weighed2CO3And 70g of NaOH is completely dissolved in 1L of water to obtain a mixed solution II; and slowly dripping the two mixed solutions into 200mL of water at the same time, violently stirring, keeping the pH value at 10 at the rotation speed of 600r/min, transferring the obtained colloidal suspension into an oven after dripping is finished, aging for 72h at 65 ℃, cooling, washing with distilled water to be neutral, drying to obtain Ni-based hydrotalcite, and further roasting the obtained Ni-based hydrotalcite precursor for 4h at 500 ℃ to obtain the high-dispersion Ni-based catalyst.
Example 2 preparation of NiMgAl-02 catalyst with hydrotalcite as precursor, (Ni)2++Mg2+)：Al3+The ratio of (A) to (B) is 3:1, Ni2+：Mg2+The ratio of (A) to (B) is 1.0.
52.34gNi(NO3)2·6H2O，46.89gAl(NO3)3·9H2O and 46.15gMg (NO)3)2·6H2Completely dissolving O in 500ml of water to obtain a mixed solution I; 26.5g Na were weighed2CO3And 70g of NaOH is completely dissolved in 1L of water to obtain a mixed solution II; and slowly dripping the two mixed solutions into 200mL of water at the same time, violently stirring, keeping the pH value at 10 at the rotation speed of 600r/min, transferring the obtained colloidal suspension into an oven after dripping is finished, aging for 72h at 65 ℃, cooling, washing with distilled water to be neutral, drying to obtain Ni-based hydrotalcite, and further roasting the obtained Ni-based hydrotalcite precursor for 4h at 500 ℃ to obtain the high-dispersion Ni-based catalyst.
EXAMPLE 3 preparation of NiMgAl-03 catalyst with hydrotalcite as precursor, (Ni)2++Mg2+)：Al3+The ratio of (A) to (B) is 3:1, Ni2+：Mg2+Is 3.0
78.52gNi(NO3)2·6H2O，46.89gAl(NO3)3·9H2O and 23.07gMg (NO)3)2·6H2Completely dissolving O in 500ml of water to obtain a mixed solution I; 26.5g Na were weighed2CO3And 70g of NaOH is completely dissolved in 1L of water to obtain a mixed solution II; and slowly dripping the two mixed solutions into 200mL of water at the same time, violently stirring, keeping the pH value at 10 at the rotation speed of 600r/min, transferring the obtained colloidal suspension into an oven after dripping is finished, aging for 72h at 65 ℃, cooling, washing with distilled water to be neutral, drying to obtain Ni-based hydrotalcite, and further roasting the obtained Ni-based hydrotalcite precursor for 4h at 500 ℃ to obtain the high-dispersion Ni-based catalyst.
EXAMPLE 4 preparation of NiMgAl-04 catalyst from hydrotalcite precursor, (Ni)2++Mg2+)：Al3+The ratio of (A) to (B) is 3:1, Ni2+：Mg2+Has a ratio of 6.0
89.73gNi(NO3)2·6H2O，46.89gAl(NO3)3·9H2O and 13.18gMg (NO)3)2·6H2Completely dissolving O in 500ml of water to obtain a mixed solution I; 26.5g Na were weighed2CO3And 70g of NaOH is completely dissolved in 1L of water to obtain a mixed solution II; and slowly dripping the two mixed solutions into 200mL of water at the same time, violently stirring, keeping the pH value at 10 at the rotation speed of 600r/min, transferring the obtained colloidal suspension into an oven after dripping is finished, aging for 72h at 65 ℃, cooling, washing with distilled water to be neutral, drying to obtain Ni-based hydrotalcite, and further roasting the obtained Ni-based hydrotalcite precursor for 4h at 500 ℃ to obtain the high-dispersion Ni-based catalyst.
EXAMPLE 5 preparation of NiMgAl-05 catalyst with hydrotalcite as precursor, (Ni)2++Mg2+)：Al3+The ratio of (A) to (B) is 3:1, Ni2+：Mg2+Is 10.0
95.17gNi(NO3)2·6H2O，46.89gAl(NO3)3·9H2O and 8.39gMg (NO)3)2·6H2Completely dissolving O in 500ml of water to obtain a mixed solution I; 26.5g Na were weighed2CO3And 70g NaOH were completely dissolved in 1L of water,obtaining a mixed solution II; and slowly dripping the two mixed solutions into 200mL of water at the same time, violently stirring, keeping the pH value at 10 at the rotation speed of 600r/min, transferring the obtained colloidal suspension into an oven after dripping is finished, aging for 72h at 65 ℃, cooling, washing with distilled water to be neutral, drying to obtain Ni-based hydrotalcite, and further roasting the obtained Ni-based hydrotalcite precursor for 4h at 500 ℃ to obtain the high-dispersion Ni-based catalyst.
EXAMPLE 6 preparation of NiZnAl-01 catalyst with hydrotalcite as precursor, (Ni)2++Zn2+)：Al3+The ratio of (A) to (B) is 2:1, Ni2+：Zn2+The ratio of (1): 1
36.34gNi(NO3)2·6H2O，40.39g Al(NO3)3·9H2O and 37.19g Zn (NO)3)2·6H2Completely dissolving O in 500ml of water to obtain a mixed solution I; 26.5g Na were weighed2CO3And 70g NaOH is completely dissolved in 1L of water to obtain a mixed solution II; and slowly dripping the two mixed solutions into 200mL of water at the same time, violently stirring, keeping the pH value at 10 at the rotation speed of 600r/min, transferring the obtained colloidal suspension into an oven after dripping is finished, aging for 72h at 65 ℃, cooling, washing with distilled water to be neutral, drying to obtain Ni-based hydrotalcite, and further roasting the obtained Ni-based hydrotalcite precursor for 4h at 500 ℃ to obtain the high-dispersion Ni-based catalyst.
EXAMPLE 7 preparation of NiCoFe-01 catalyst with hydrotalcite as precursor, (Ni)2++Co2+)：Fe3+The ratio of (1): 1, Ni2+：Co 2+The ratio of (A) to (B) is 3:1
21.8g Ni(NO3)2·6H2O，40.39g Fe(NO3)3·9H2O and 7.27g Co (NO)3)2·6H2Completely dissolving O in 500ml of water to obtain a mixed solution I; 26.5g Na were weighed2CO3And 70g NaOH is completely dissolved in 1L of water to obtain a mixed solution II; slowly adding the two mixed solutions into 200mL of water, stirring vigorously at 600r/min, maintaining pH at 10, transferring the obtained colloidal suspension into an oven, aging at 65 deg.C for 72 hr, cooling, and steamingWashing the distilled water to be neutral, drying to obtain Ni-based hydrotalcite, and further roasting the obtained Ni-based hydrotalcite precursor at 500 ℃ for 4h to obtain the high-dispersion Ni-based catalyst.
Example 8 alkaline earth metal modified NiMgAl catalyst
0.89gMg (CH)3COO)2·4H2Dissolving O in water, metering to 15mL, taking 10g of NiMgAl-03 catalyst (namely the high-dispersion Ni-based catalyst provided in the embodiment 3), loading Mg on the NiMgAl catalyst by adopting an isometric impregnation method, placing the NiMgAl catalyst in a 100 ℃ oven for drying for 12h, and then roasting the NiMgAl catalyst in a 500 ℃ muffle furnace for 4h to obtain the alkaline earth metal modified NiMgAl catalyst which is marked as 1.0 Mg/NiMgAl-03.
Examples 9-18 alkaline earth metal-modified NiMgAl catalysts
The method provided in example 8 was used to prepare an alkaline earth metal modified NiMgAl catalyst by replacing the NiMgAl catalyst (i.e., the highly dispersed Ni-based catalyst provided in examples 1 to 5) and the type and content of the alkaline earth metal salt, and the specific preparation conditions are shown in table 2.
Table 2 preparation parameters of the catalysts of examples 8-18
In the catalysts nA/B, n represents a metal loading amount, A represents a loaded metal, and B represents a catalyst (provided in examples 1 to 7).
EXAMPLES 19-30 evaluation of reactivity of catalysts
Filling 2.0g of the catalyst into a small-sized fixed bed reactor, wherein the small-sized fixed bed reactor is a stainless steel reaction tube with the inner diameter of 10mm and the length of 300mm, filling quartz sand at two ends of the catalyst, firstly introducing reducing gas at the flow rate of 30mL/min, and carrying out reduction treatment on the catalyst for 4 hours at the temperature of 400 ℃, wherein the reducing gas is H2/N21/4 by volume ratio.
After the reduction is finished, the temperature of the reactor is reduced to the reaction temperature, the reactor is pressurized to the reaction pressure, and H is respectively introduced into the reactor2And liquid ammonia and hexanedial are subjected to reductive amination reaction, wherein the liquid ammonia and the hexanedial are respectively injected into the reactor through a high-pressure trace feed pump, the reaction is carried out for 10 hours, sampling analysis is carried out, and the reaction results are listed in Table 3.
Wherein the adipaldehyde is provided in examples 1 '-11', and the reaction results of the adipaldehyde obtained in each example are consistent.
Table 3 reactivity of catalysts prepared in example 3, examples 8-18
As can be seen from Table 3, the catalyst provided by each embodiment of the invention has excellent selectivity on hexamethylene diamine in the reaction of preparing hexanediamine by reductive amination of hexanediamine, wherein the selectivity of the hexanediamine can reach 87.3 percent at most, and the conversion rate of the hexanediamine can reach 99.7 percent at most; example 19 shows a NiMgAl catalyst that is not modified with an alkaline earth metal, where the selectivity of hexamethylenediamine in the reaction of reductive amination of hexanedial to produce hexanediamine is only 35.4%, which is much lower than that of the catalyst modified with an alkaline earth metal, and further demonstrates that the catalyst prepared by modifying with an alkaline earth metal to adjust the acidity or basicity of the catalyst has both the characteristics of metal catalysis and basic catalysis, and shows good activity and selectivity when applied to the reductive amination of hexanedial.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
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