CN106242947A - A kind of method utilizing cerium modified zirconium-silicon molecular sieve catalyst to prepare dichlorohydrin - Google Patents
A kind of method utilizing cerium modified zirconium-silicon molecular sieve catalyst to prepare dichlorohydrin Download PDFInfo
- Publication number
- CN106242947A CN106242947A CN201610625888.7A CN201610625888A CN106242947A CN 106242947 A CN106242947 A CN 106242947A CN 201610625888 A CN201610625888 A CN 201610625888A CN 106242947 A CN106242947 A CN 106242947A
- Authority
- CN
- China
- Prior art keywords
- glycerol
- molecular sieve
- cerium modified
- silicon molecular
- zirconium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 33
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 30
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 30
- UVGLBOPDEUYYCS-UHFFFAOYSA-N silicon zirconium Chemical class [Si].[Zr] UVGLBOPDEUYYCS-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 229910052684 Cerium Inorganic materials 0.000 title claims abstract description 22
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims abstract description 22
- DEWLEGDTCGBNGU-UHFFFAOYSA-N 1,3-dichloropropan-2-ol Chemical compound ClCC(O)CCl DEWLEGDTCGBNGU-UHFFFAOYSA-N 0.000 title claims abstract description 17
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 139
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 230000004044 response Effects 0.000 claims abstract description 19
- 239000006227 byproduct Substances 0.000 claims abstract description 9
- 238000002360 preparation method Methods 0.000 claims abstract description 8
- 239000003225 biodiesel Substances 0.000 claims abstract description 6
- 239000006096 absorbing agent Substances 0.000 claims abstract description 3
- 239000011552 falling film Substances 0.000 claims abstract description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 8
- 229910007735 Zr—Si Inorganic materials 0.000 claims description 8
- 230000032683 aging Effects 0.000 claims description 8
- 229910021529 ammonia Inorganic materials 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000000376 reactant Substances 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 4
- 238000002425 crystallisation Methods 0.000 claims description 4
- 230000008025 crystallization Effects 0.000 claims description 4
- 239000012153 distilled water Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000012065 filter cake Substances 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- 239000003921 oil Substances 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims 1
- 235000009508 confectionery Nutrition 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 230000003213 activating effect Effects 0.000 abstract description 2
- 230000001172 regenerating effect Effects 0.000 abstract description 2
- 235000011187 glycerol Nutrition 0.000 description 36
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 11
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 10
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 9
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 238000005660 chlorination reaction Methods 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- 229910002492 Ce(NO3)3·6H2O Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- KNKRKFALVUDBJE-UHFFFAOYSA-N 1,2-dichloropropane Chemical compound CC(Cl)CCl KNKRKFALVUDBJE-UHFFFAOYSA-N 0.000 description 2
- DYPJJAAKPQKWTM-UHFFFAOYSA-N 2-chloropropane-1,3-diol Chemical compound OCC(Cl)CO DYPJJAAKPQKWTM-UHFFFAOYSA-N 0.000 description 2
- SSZWWUDQMAHNAQ-UHFFFAOYSA-N 3-chloropropane-1,2-diol Chemical compound OCC(O)CCl SSZWWUDQMAHNAQ-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- MLHOXUWWKVQEJB-UHFFFAOYSA-N Propyleneglycol diacetate Chemical compound CC(=O)OC(C)COC(C)=O MLHOXUWWKVQEJB-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- ZXCYIJGIGSDJQQ-UHFFFAOYSA-N 2,3-dichloropropan-1-ol Chemical compound OCC(Cl)CCl ZXCYIJGIGSDJQQ-UHFFFAOYSA-N 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/62—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by introduction of halogen; by substitution of halogen atoms by other halogen atoms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
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 relates to a kind of method utilizing cerium modified zirconium-silicon molecular sieve catalyst to prepare dichlorohydrin, comprise the steps: to be placed in primary response still glycerol and cerium modified zirconium-silicon molecular sieve catalyst, it is heated to 90 125 DEG C, HCl gas is compressed enters primary response bottom portion by gas distributor, react 3 10h, unreacted HCl gas enters pre-reactor after primary response still top is flowed out, and reacts with glycerol at 50 90 DEG C；The a small amount of HCl gas discharged by pre-reactor is absorbed by falling-film absorber.Cerium modified zirconium-silicon molecular sieve method for preparing catalyst of the present invention is simple, and catalytic efficiency is high, and the usage amount of catalyst is few, and catalytic life is longer, it is possible to carry out activating and regenerating use；Purity requirement for glycerol is relatively low, and reaction glycerol used can be the by-product glycerol that the purity obtained in preparation of biodiesel is relatively low；The dichlorohydrin selectivity of the present invention is good, and the conversion ratio of glycerol is high.
Description
Technical field
The present invention relates to a kind of method for preparing dichlorohydrin, especially one and utilize cerium modified zirconium-silicon molecular sieve catalyst system
The method of standby dichlorohydrin.
Background technology
Dichlorohydrin (referred to as DCH) is colourless liquid, has 1,3-dichlorohydrin and 2, two kinds of isomeries of 3-dichlorohydrin
Body, they are as the intermediate of synthesizing epoxy chloropropane, all can carry out saponification with the alkali liquor such as lime water or sodium hydroxide, de-
A part hydrogen chloride, cyclisation is gone to generate epoxychloropropane.Epoxychloropropane is a kind of important Organic Chemicals and becomes more meticulous
Chemical product, main application propylene high-temperature chloridising and two kinds of techniques of propylene acetate method in current commercial production.Both approaches
Core procedure be all utilize propylene for initial feed, with chlorine as chloridric medium, generate intermediate DCH.High-temperature chlorination sets
Standby seriously corroded, energy consumption is big, and chlorine consumption is high, and by-product is many, and processing cost is high, and product yield is relatively low；And propylene acetate method work
Process flow is longer, and catalyst life is short, and investment cost is of a relatively high.And as the propylene of initial feed along with petroleum resources
Consume growing tension, limit the further development of epoxychloropropane.
Current along with biodiesel development, the glycerol of its by-product also relative surplus.Utilize glycerol and hydrochloric acid or chlorination
Hydrogen is synthesized intermediate DCH, and the Appropriate application for glycerol provides a kind of new way, also reduces disappearing of propylene simultaneously
Consumption；Secondly, high-temperature chlorination mainly synthesizes the 2 of 70%, 3-dichlorohydrin and the 1 of 30%, the two kinds of isomers of 3-dichlorohydrin, and
Utilize the DCH that glycerin chlorination synthesizes, mostly 1,3-dichlorohydrin, this isomer relative to 2,3-dichlorohydrin,
During synthesizing epoxy chloropropane, response speed is very fast, and yield is higher；Further, since glycerol method raw material does not use chlorine
Gas, also reduces environmental pollution to a certain extent.
In fact, during being originally found epoxychloropropane, it is simply that make use of the reaction of glycerol synthesis DCH.1854,
Berthelot utilizes HCl treatment crude glycerine, has then first synthesized epoxychloropropane with alkali liquor hydrolysis.After several years, Reboul
Propose epoxychloropropane to be reacted with sodium hydroxide solution by DCH and directly produce.It is directly synthesized grinding of DCH subsequently, for glycerol
Studying carefully and increasingly come into one's own, the emphasis of research includes developing various catalyst to improve glycerol conversion yield, and utilizes suitably
Extractant increases the yield (amount of the DCH material obtained is relative to the percentage ratio of the amount of raw materials glycerine material) of DCH.
Although the research utilizing glycerol to be directly synthesized DCH achieves the highest yield more already, but between great majority are
Formula of having a rest is reacted, and the response time is relatively long.Expensive plus glycerol in early days, this research not large-scale practical application.
Prepare the heavy industrialization application of biodiesel recently as natural oil, the Utilizing question of by-product glycerin goes out therewith
Existing.People just restudy and utilize glycerol to prepare DCH.Glycerol price is low at present, and epoxychloropropane price one tunnel is high, with
Glycerol is that the route of raw material production epoxychloropropane gradually moves towards commercial Application.
Summary of the invention
On the basis of existing technology, emphasis improves catalysts to the present invention, no longer makees with traditional organic carboxyl acid
For catalyst, thus reducing later separation difficulty, thus reduce production cost, final realization produces continuously.ZrO2It is to have
Surface acidity position and the transition metal oxide of basic sites, have excellent ion-exchange performance, both can be single at catalytic field
Solely use as catalyst, it is also possible to as catalyst carrier or auxiliary agent.If the pore structure giving its prosperity not only contributes to
Electric charge, in alternate transmission, improves its charge transfer performance, and can reduce reactant molecule or product molecule at catalyst
In diffusional resistance, thus improve and optimize its catalytic perfomance.But compared with mesoporous silicon sill, ZrO2Heat stability
Poor.The present invention carries out modulation by introducing its acidity of metal zirconium atom pair in silicon-based mesoporous molecular sieve, and introduces metallic cerium
Adjust its acid intensity and charge transfer, be prepared for can be used for glycerol and prepare the effective catalyst of dichlorohydrin.
A kind of method utilizing cerium modified zirconium-silicon molecular sieve catalyst to prepare dichlorohydrin, comprises the steps: glycerol
Being placed in primary response still with cerium modified zirconium-silicon molecular sieve catalyst, be heated to 90-125 DEG C, HCl gas is compressed to be divided by gas
Cloth device enters primary response bottom portion, reacts 3-10h, and unreacted HCl gas enters pre-reaction after primary response still top is flowed out
In device, react with glycerol at 50-90 DEG C；The a small amount of HCl gas discharged by pre-reactor is inhaled by falling-film absorber
Receive.
Product in described pre-reactor is sent in primary response still react further.
The addition of described cerium modified zirconium-silicon molecular sieve catalyst is the 0.05-0.3%, preferably 0.1-of qualities of glycerin
0.2%.
Described HCl is 3-10:1 with the mol ratio of glycerol, preferably 3-5:1.
Described glycerol can be prepared by the glycerol of the glycerol that purity is relatively low, preferably 50wt%, especially biodiesel
The by-product glycerol obtained in journey.
The preparation method of described cerium modified zirconium-silicon molecular sieve catalyst, comprises the following steps:
Zirconium nitrate and cetyl trimethylammonium bromide (CTAB) are dissolved in deionized water by 1:0.5-2 in molar ratio.
Zirconium silicon drips tetraethyl orthosilicate than 1:2-4 again, and preferably zirconium silicon is than 1:3, stirs aging 6-12h after dropping；Then ammonia is used
Regulation pH value to 10-12, after stirring 12-24h in reactant reaction still in 100-120 DEG C of crystallization 48-72h, then filter, use
Deionized water wash to neutral, after drying at 400-500 DEG C roasting 6-12h, obtain mesoporous Zr-Si molecular sieve；
By Ce (NO3)3·6H2O is dissolved in distilled water, adds mesoporous Zr-Si molecular sieve, then with ammonia as precipitant, control
PH value processed is at 10-11；3-12h is stirred aging at 110-140 DEG C；Then sucking filtration, washing precipitation are carried out；By filter cake at 120-
It is dried 5-24h at 150 DEG C, is placed in Muffle furnace at 350-500 DEG C of roasting 6-12h, it is thus achieved that cerium modified zirconium-silicon molecular sieve catalyst
Finished product.
Because glycerol is the gentleest with the first step reaction condition of HCl, response speed is very fast, uses unreacted HCl gas
The method that body and glycerol react in pre-reactor, can reduce energy consumption with the heat of Appropriate application unreacted HCl gas, again may be used
To shorten the response time.
The present invention compared with prior art, has the advantage that cerium modified zirconium-silicon molecular sieve catalyst system of the present invention
Preparation Method is simple, and catalytic efficiency is high, and the usage amount of catalyst is few, and catalytic life is longer, it is possible to carry out activating and regenerating use,
Wherein 1, the yield of 3-DCP can reach more than 85%, and the conversion ratio of glycerol is 100%；Purity requirement for glycerol is relatively low,
Reaction glycerol used can be the by-product glycerol that the purity obtained in preparation of biodiesel is relatively low；The dichlorohydrin of the present invention
Selectivity is good, and the conversion ratio of glycerol is high.
Detailed description of the invention
Embodiment
Embodiment 1
The preparation of cerium modified zirconium-silicon molecular sieve catalyst
Zirconium nitrate and cetyl trimethylammonium bromide (CTAB) are dissolved in deionized water by 1:1 in molar ratio.Zirconium again
Silicon drips tetraethyl orthosilicate than 1:2, stirs aging 12h after dropping；Then with ammonia regulation pH value to 11, after stirring 12h
In reactant reaction still in 120 DEG C of crystallization 48h, then filter, be washed with deionized to neutrality, after drying at 400 DEG C
Roasting 12h, obtains mesoporous Zr-Si molecular sieve；
By Ce (NO3)3·6H2O is dissolved in distilled water, adds mesoporous Zr-Si molecular sieve, then with ammonia as precipitant, control
PH value processed is 10；6h is stirred aging at 110 DEG C；Then sucking filtration, washing precipitation are carried out；Filter cake is dried at 120 DEG C 12h,
It is placed in Muffle furnace at 400 DEG C of roasting 6h, it is thus achieved that cerium modified zirconium-silicon molecular sieve finished catalyst.
Preparing dichloropropane reaction with above-mentioned catalyst glycerol, the response time is 6h, the receipts at a temperature of differential responses
Rate is as follows:
| Reaction temperature | Glycerol conversion yield | 2-MCPD yield | 3-MCPD yield | 1,3-DCP yield | 1,3-DCP yield | By-product yield |
| 95℃ | 100 | 2.61 | 8.42 | 85.06 | 2.69 | 1.22 |
| 105℃ | 100 | 1.95 | 5.92 | 88.10 | 2.86 | 1.17 |
| 115℃ | 100 | 1.58 | 2.55 | 92.11 | 2.53 | 1.23 |
Embodiment 2
The preparation of cerium modified zirconium-silicon molecular sieve catalyst
Zirconium nitrate and cetyl trimethylammonium bromide (CTAB) are dissolved in deionized water by 1:2 in molar ratio.Zirconium again
Silicon drips tetraethyl orthosilicate than 1:4, stirs aging 6h after dropping；Then with ammonia regulation pH value to 12, handle after stirring 24h
In 120 DEG C of crystallization 72h in reactant reaction still, then filter, be washed with deionized to neutrality, roast at 500 DEG C after drying
Burn 12h, obtain mesoporous Zr-Si molecular sieve；
By Ce (NO3)3·6H2O is dissolved in distilled water, adds mesoporous Zr-Si molecular sieve, then with ammonia as precipitant, control
PH value processed is 11；12h is stirred aging at 140 DEG C；Then sucking filtration, washing precipitation are carried out；Filter cake is dried at 150 DEG C 6h,
It is placed in Muffle furnace at 500 DEG C of roasting 6h, it is thus achieved that cerium modified zirconium-silicon molecular sieve finished catalyst.
Preparing dichloropropane reaction with above-mentioned catalyst glycerol, the response time is 9h, the receipts at a temperature of differential responses
Rate is as follows:
| Reaction temperature | Glycerol conversion yield | 2-MCPD yield | 3-MCPD yield | 1,3-DCP yield | 1,3-DCP yield | By-product yield |
| 95℃ | 100 | 2.32 | 7.25 | 86.89 | 2.17 | 1.37 |
| 105℃ | 100 | 1.38 | 4.23 | 90.68 | 1.96 | 1.75 |
| 115℃ | 100 | 0.85 | 2.57 | 92.79 | 2.03 | 1.76 |
Above example is only the preferred embodiment of the present invention, but the present invention is not limited to above-mentioned embodiment,
In the case of the flesh and blood of the present invention, those skilled in the art can make any conspicuously improved, replace
Change or modification is the most within the scope of the present invention.
Claims (8)
1. the method utilizing cerium modified zirconium-silicon molecular sieve catalyst to prepare dichlorohydrin, comprise the steps: by glycerol with
Cerium modified zirconium-silicon molecular sieve catalyst is placed in primary response still, is heated to 90-125 DEG C, and HCl gas is compressed to be distributed by gas
Device enters primary response bottom portion, reacts 3-10h, and unreacted HCl gas enters pre-reactor after primary response still top is flowed out
In, react with glycerol at 50-90 DEG C；The a small amount of HCl gas discharged by pre-reactor is absorbed by falling-film absorber.
2. the method for claim 1, it is characterised in that the product in described pre-reactor is sent to primary response still
In react further.
3. the method for claim 1, it is characterised in that the addition of described cerium modified zirconium-silicon molecular sieve catalyst is sweet
The 0.05-0.3% of oil quality, preferably 0.1-0.2%.
4. the method for claim 1, it is characterised in that described HCl is 3-10:1 with the mol ratio of glycerol, preferably 3-
5:1。
5. the method for claim 1, it is characterised in that the preparation method of described cerium modified zirconium-silicon molecular sieve catalyst, bag
Include following steps:
Zirconium nitrate and cetyl trimethylammonium bromide (CTAB) are dissolved in deionized water by 1:0.5-2 in molar ratio.Zirconium again
Silicon drips tetraethyl orthosilicate than 1:2-4, stirs aging 6-12h after dropping；Then with ammonia regulation pH value to 10-12, stir
Mix after 12-24h in reactant reaction still in 100-120 DEG C of crystallization 48-72h, then filter, be washed with deionized in
Property, after drying at 400-500 DEG C roasting 6-12h, obtain mesoporous Zr-Si molecular sieve；
Ce (NO3) 3 6H2O is dissolved in distilled water, adds mesoporous Zr-Si molecular sieve, then with ammonia as precipitant, control pH
Value is at 10-11；3-12h is stirred aging at 110-140 DEG C；Then sucking filtration, washing precipitation are carried out；By filter cake at 120-150 DEG C
Under be dried 5-24h, be placed in Muffle furnace at 350-500 DEG C of roasting 6-12h, it is thus achieved that cerium modified zirconium-silicon molecular sieve finished catalyst.
6. method as claimed in claim 5, it is characterised in that described zirconium silicon compares 1:3.
7. the method for claim 1, it is characterised in that described glycerol is the purity obtained in preparation of biodiesel
Relatively low by-product glycerol.
8. the method for claim 1, it is characterised in that the concentration of described glycerol is more than 50wt%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610625888.7A CN106242947B (en) | 2016-08-02 | 2016-08-02 | A kind of method using cerium modified zirconium-silicon molecular sieve catalyst preparation dichlorohydrin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610625888.7A CN106242947B (en) | 2016-08-02 | 2016-08-02 | A kind of method using cerium modified zirconium-silicon molecular sieve catalyst preparation dichlorohydrin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106242947A true CN106242947A (en) | 2016-12-21 |
| CN106242947B CN106242947B (en) | 2018-07-10 |
Family
ID=57607120
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610625888.7A Active CN106242947B (en) | 2016-08-02 | 2016-08-02 | A kind of method using cerium modified zirconium-silicon molecular sieve catalyst preparation dichlorohydrin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106242947B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108689850A (en) * | 2018-07-01 | 2018-10-23 | 北京化工大学 | A kind of method of cerium zirconium oxide/molecular sieve catalytic synthesizing diethyl carbonate |
| CN109261118A (en) * | 2018-09-03 | 2019-01-25 | 扬州大学 | A kind of preparation method of cerium, zirconium double metal modified SBA-15 desulfuration adsorbent |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101024187A (en) * | 2007-03-24 | 2007-08-29 | 太原理工大学 | Super-strong acid mesoporous material synthesized in one pot and preparing method |
| CN103111326A (en) * | 2013-03-11 | 2013-05-22 | 南京工业大学 | Carboxylic acid group functionalization SBA molecular sieve based catalyst for synthesizing dichloropropanol through glycerol hydrochlorination |
| CN104151139A (en) * | 2014-07-24 | 2014-11-19 | 江苏大学 | Method for preparing dichlorohydrin through glycerinum chlorination under catalysis of HY type molecular sieve |
| CN104163753A (en) * | 2014-07-24 | 2014-11-26 | 江苏大学 | Method for preparing dichloropropanol by modified L-type molecular sieve-catalytic chlorination of glycerin |
| CN104492473A (en) * | 2014-12-30 | 2015-04-08 | 华东理工大学 | Molecular sieve-coating cerium oxide composite material and preparation method thereof |
| CN105344372A (en) * | 2015-11-09 | 2016-02-24 | 太原理工大学 | Preparation device and preparation method for mesoporous zirconium-based molecular sieve catalyst |
-
2016
- 2016-08-02 CN CN201610625888.7A patent/CN106242947B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101024187A (en) * | 2007-03-24 | 2007-08-29 | 太原理工大学 | Super-strong acid mesoporous material synthesized in one pot and preparing method |
| CN103111326A (en) * | 2013-03-11 | 2013-05-22 | 南京工业大学 | Carboxylic acid group functionalization SBA molecular sieve based catalyst for synthesizing dichloropropanol through glycerol hydrochlorination |
| CN104151139A (en) * | 2014-07-24 | 2014-11-19 | 江苏大学 | Method for preparing dichlorohydrin through glycerinum chlorination under catalysis of HY type molecular sieve |
| CN104163753A (en) * | 2014-07-24 | 2014-11-26 | 江苏大学 | Method for preparing dichloropropanol by modified L-type molecular sieve-catalytic chlorination of glycerin |
| CN104492473A (en) * | 2014-12-30 | 2015-04-08 | 华东理工大学 | Molecular sieve-coating cerium oxide composite material and preparation method thereof |
| CN105344372A (en) * | 2015-11-09 | 2016-02-24 | 太原理工大学 | Preparation device and preparation method for mesoporous zirconium-based molecular sieve catalyst |
Non-Patent Citations (3)
| Title |
|---|
| 卢德庆等: ""甘油合成二氯丙醇的研究进展"", 《山东化工》 * |
| 李刚: ""含锆分子筛的合成及其催化性能研究"", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
| 董作为: ""介孔氧化硅分子筛的合成及其锆离子催化改性"", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108689850A (en) * | 2018-07-01 | 2018-10-23 | 北京化工大学 | A kind of method of cerium zirconium oxide/molecular sieve catalytic synthesizing diethyl carbonate |
| CN109261118A (en) * | 2018-09-03 | 2019-01-25 | 扬州大学 | A kind of preparation method of cerium, zirconium double metal modified SBA-15 desulfuration adsorbent |
| CN109261118B (en) * | 2018-09-03 | 2022-02-08 | 扬州大学 | Preparation method of cerium and zirconium bimetal modified SBA-15 desulfurization adsorbent |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106242947B (en) | 2018-07-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103539700B (en) | Preparation method of N-cyanoethylaniline | |
| CN106242947B (en) | A kind of method using cerium modified zirconium-silicon molecular sieve catalyst preparation dichlorohydrin | |
| CN102304024B (en) | Method for synthesizing difluoroethanol | |
| CN101455976A (en) | Effective catalyst used in hydrogenation of dimethyl oxalate to synthesizing ethylene glycol and production method thereof | |
| CN106316810B (en) | A kind of preparation method improving 1,1,3- trichloroacetone synthesis yields | |
| CN113603574B (en) | Method for catalyzing catalytic oxidation reaction of cyclopentene by using short-site silicotungstic heteropolyacid salt catalyst | |
| CN105732439A (en) | Multi-sulfonic-acid-group acidic functionalized ionic liquid and preparation method thereof | |
| CN101704823B (en) | Method for preparing bicyclopentadiene dioxide by catalysis through emulsion method | |
| CN103012114A (en) | Method of synchronously preparing DL-tartaric acid and DL-potassium hydrogen tartrate | |
| CN107954919A (en) | A kind of preparation method of Rucaparib key intermediates | |
| CN104496825B (en) | The preparation method of 2-fluorine ethylamine hydrochloride | |
| CN110938470A (en) | Method for producing chlorinated paraffin-70 by low-temperature catalysis | |
| CN103965094B (en) | The synthetic method of the N-methyl-4-bromo-phthalimide of amino-5- | |
| CN110013875A (en) | A kind of preparation method of fluorine richness molecular sieve FER | |
| CN108863997A (en) | A kind of preparation method of 5 methyl furfural | |
| CN101531831B (en) | Production method of direct blended brown D-RS dye | |
| CN106140197A (en) | Solid super acid catalyst and preparation method thereof and the isomerization method of light normal paraffin | |
| CN1508113A (en) | Industrial method for preparing beta-ionone | |
| CN109746047B (en) | Preparation and application of bifunctional three-phase transfer catalyst | |
| CN105032483B (en) | Synthesize catalyst of N methyl alcamine compounds and preparation method thereof, application | |
| CN101774882A (en) | Method for catalytic hydrodechlorination of CFC125 into HFC-125 | |
| CN1190398C (en) | Process for preparing bromo-n-dodecane | |
| CN110372740A (en) | A kind of method that dimethylchlorosilane prepares trim,ethylchlorosilane | |
| CN104592034A (en) | Synthetic method of 1, 3-diamidophenyl-5, 7-dimethyl adamantane | |
| CN109046335A (en) | A kind of preparation method synthesizing 1,1,2,2- tetrafluoroethane catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CB03 | Change of inventor or designer information | ||
| CB03 | Change of inventor or designer information |
Inventor after: Ma Wansheng Inventor after: Cheng Mingguang Inventor after: Cheng Pengfei Inventor after: Wang Huiqin Inventor after: Xie Guizhi Inventor before: Ma Wansheng Inventor before: Cheng Mingguang Inventor before: Cheng Pengfei |
|
| CP03 | Change of name, title or address |
Address after: 245061 Changsheng Road, Yao Cun village, Yansi Town, Huizhou District, Huangshan City, Anhui, 11 Patentee after: Mount Huangshan Tianma new Mstar Technology Ltd Address before: 245061 2 Jetta Road, Chengdong Industrial Park, Huizhou District, Huangshan City, Anhui Patentee before: Huangshan Huizhou Tianma Chemical Co., Ltd. |
|
| CP03 | Change of name, title or address | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Method for preparing dichloropropanol by utilization of cerium-modified zironosilicate molecular sieve catalyst Effective date of registration: 20180929 Granted publication date: 20180710 Pledgee: Huizhou Mount Huangshan rural commercial bank Limited by Share Ltd Pledgor: Mount Huangshan Tianma new Mstar Technology Ltd Registration number: 2018340000519 |
|
| PC01 | Cancellation of the registration of the contract for pledge of patent right | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Date of cancellation: 20191028 Granted publication date: 20180710 Pledgee: Huizhou Mount Huangshan rural commercial bank Limited by Share Ltd Pledgor: Mount Huangshan Tianma new Mstar Technology Ltd Registration number: 2018340000519 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Method for preparing dichloropropanol by utilization of cerium-modified zironosilicate molecular sieve catalyst Effective date of registration: 20191230 Granted publication date: 20180710 Pledgee: Tunxi Mount Huangshan rural commercial bank Limited by Share Ltd Pledgor: Mount Huangshan Tianma new Mstar Technology Ltd Registration number: Y2019340000243 |
|
| PC01 | Cancellation of the registration of the contract for pledge of patent right | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Date of cancellation: 20210317 Granted publication date: 20180710 Pledgee: Tunxi Mount Huangshan rural commercial bank Limited by Share Ltd. Pledgor: HUANGSHAN TIANMA NEW MATERIAL TECHNOLOGY Co.,Ltd. Registration number: Y2019340000243 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: A method for preparing dichloropropanol using cerium modified zirconium silicon molecular sieve catalyst Effective date of registration: 20220224 Granted publication date: 20180710 Pledgee: Qimen Anhui rural commercial bank Limited by Share Ltd. Pledgor: HUANGSHAN TIANMA NEW MATERIAL TECHNOLOGY CO.,LTD. Registration number: Y2022980001772 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right |