CN106242947B - A kind of method using cerium modified zirconium-silicon molecular sieve catalyst preparation dichlorohydrin - Google Patents
A kind of method using cerium modified zirconium-silicon molecular sieve catalyst preparation dichlorohydrin Download PDFInfo
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- CN106242947B CN106242947B CN201610625888.7A CN201610625888A CN106242947B CN 106242947 B CN106242947 B CN 106242947B CN 201610625888 A CN201610625888 A CN 201610625888A CN 106242947 B CN106242947 B CN 106242947B
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- 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 27
- 238000000034 method Methods 0.000 title claims abstract description 23
- 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
- DEWLEGDTCGBNGU-UHFFFAOYSA-N 1,3-dichloropropan-2-ol Chemical compound ClCC(O)CCl DEWLEGDTCGBNGU-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 105
- 235000011187 glycerol Nutrition 0.000 claims abstract description 49
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 239000007789 gas Substances 0.000 claims abstract description 15
- 239000006227 byproduct Substances 0.000 claims abstract description 9
- 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 8
- 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
- 239000000908 ammonium hydroxide Substances 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
- 239000000376 reactant Substances 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 229910002492 Ce(NO3)3·6H2O Inorganic materials 0.000 claims description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 4
- 238000003483 aging Methods 0.000 claims description 4
- 239000003153 chemical reaction reagent Substances 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
- 239000012065 filter cake Substances 0.000 claims description 4
- 230000001376 precipitating effect Effects 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 239000003921 oil Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 235000009508 confectionery Nutrition 0.000 claims 2
- 238000010025 steaming Methods 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
- 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
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 9
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 8
- 238000005660 chlorination reaction Methods 0.000 description 4
- 239000000047 product Substances 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
- 230000035484 reaction time Effects 0.000 description 4
- 235000011121 sodium hydroxide Nutrition 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 239000000543 intermediate Substances 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
- 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
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000036632 reaction speed Effects 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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical group [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process 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
- 238000009776 industrial production Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material 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
- 239000003208 petroleum Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002243 precursor Substances 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
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 229910052726 zirconium 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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a kind of methods using cerium modified zirconium-silicon molecular sieve catalyst preparation dichlorohydrin, include the following steps：Glycerine and cerium modified zirconium-silicon molecular sieve catalyst are placed in main reaction kettle, it is heated to 90 125 DEG C, HCl gases are compressed to enter main reaction bottom portion by gas distributor, react 3 10h, unreacted HCl gases enter after being flowed out from main reaction kettle top portion in pre-reactor, are reacted at 50 90 DEG C with glycerine；The a small amount of HCl gases discharged by pre-reactor are absorbed by falling-film absorber.Cerium modified zirconium-silicon molecular sieve method for preparing catalyst of the present invention is simple, and high catalytic efficiency, the usage amount of catalyst is few, and catalytic life is longer, and can carry out activating and regenerating use；Relatively low for the purity requirement of glycerine, glycerine used in reaction can be the relatively low by-product glycerol of the purity obtained in preparation of biodiesel；The dichlorohydrin of the present invention is selectively good, the high conversion rate of glycerine.
Description
Technical field
The present invention relates to a kind of method for preparing dichlorohydrin, especially a kind of to 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 two kinds of isomeries of 1,3- dichlorohydrins and 2,3- dichlorohydrin
Body, their intermediates as synthesizing epoxy chloropropane can carry out saponification with lye such as limewash or sodium hydroxides, take off
Remove a molecule hydrogen chloride, cyclisation generation epoxychloropropane.Epoxychloropropane is a kind of important Organic Chemicals and becomes more meticulous
Chemical product mainly applies two kinds of techniques of propylene high-temperature chloridising and propylene acetate method in current industrial production.Both methods
Core procedure be using propylene be initial feed, using chlorine as chloridric medium, generate intermediate DCH.High-temperature chlorination is set
Standby seriously corroded, energy consumption is big, and chlorine consumption is high, and by-product is more, and processing cost is high, and product yield is relatively low；And propylene acetate method work
Skill flow is longer, and catalyst life is short, and investment cost is relatively high.And the propylene as initial feed is with petroleum resources
Growing tension is consumed, limits the further development of epoxychloropropane.
Now as biodiesel continues to develop, the glycerine of by-product also relative surplus.Utilize glycerine and hydrochloric acid or chlorination
Hydrogen precursor reactant synthetic intermediate DCH, reasonable utilize for glycerine provide a kind of new way, while also reduce disappearing for propylene
Consumption；Secondly, high-temperature chlorination mainly synthesizes 70% 2,3- dichlorohydrins and 30% 1,3- dichlorohydrins, two kinds of isomers, and
The DCH synthesized using glycerin chlorination, mostly 1,3- dichlorohydrins, this isomers relative to 2,3- dichlorohydrins,
During synthesizing epoxy chloropropane, reaction speed is very fast, and yield is higher；In addition, use chlorine due to no in glycerine method raw material
Gas also reduces environmental pollution to a certain extent.
In fact, during epoxychloropropane is originally found, the reaction of glycerine synthesis DCH is exactly utilized.1854,
Berthelot utilizes HCl treatment crude glycerine, has then synthesized epoxychloropropane first with lye hydrolysis.After several years, Reboul
It proposes that epoxychloropropane can be reacted by DCH with sodium hydroxide solution directly to produce.Grinding for DCH is directly synthesized subsequently, for glycerine
Study carefully and be increasingly taken seriously, the emphasis of research includes developing various catalyst to improve glycerol conversion yield and utilize suitably
Extractant increases the yield of the DCH percentage of the amount of raw materials glycerine substance (the obtained amount of DCH substances relative to).
Although the research that DCH is directly synthesized using glycerine is more already achieving very high yield, it is most of be between
Formula of having a rest is reacted, and the reaction time is relatively long.In addition early stage glycerine is expensive, there is no large-scale practical applications for this research.
The heavy industrialization application of biodiesel is prepared recently as natural oil, the Utilizing question of by-product glycerin goes out therewith
It is existing.People just restudy prepares DCH using glycerine.Glycerine price is sluggish at present, and epoxychloropropane price is high all the way, with
The route that glycerine produces epoxychloropropane for raw material gradually moves towards commercial Application.
Invention content
On the basis of existing technology, emphasis improves catalysts to the present invention, is no longer made with traditional organic carboxyl acid
For catalyst, so as to reduce later separation difficulty, so as to reduce production cost, continuous production is finally realized.ZrO2It is to have
Surface acidity position and the transition metal oxide of basic sites have excellent ion-exchange performance, both can be single in catalytic field
It is solely used as catalyst, can also be used as catalyst carrier or auxiliary agent.If it assigns its flourishing pore structure to not only contribute to
Charge improves its charge transfer performance, and can reduce reactant molecule or product molecule in catalyst in alternate transmission
In diffusional resistance, so as to improve with optimize its catalytic perfomance.But compared with mesoporous silica-base material, ZrO2Thermal stability
It is poor.The present invention introduces metallic cerium by its acidity progress modulation of introducing metal zirconium atom pair in silicon-based mesoporous molecular sieve
Its acid intensity and charge transfer are adjusted, is prepared for the effective catalyst that glycerine can be used for prepare dichlorohydrin.
A kind of method using cerium modified zirconium-silicon molecular sieve catalyst preparation dichlorohydrin includes the following steps：By glycerine
It is placed in main reaction kettle with cerium modified zirconium-silicon molecular sieve catalyst, is heated to 90-125 DEG C, HCl gases are compressed to pass through gas point
Cloth device enters main reaction bottom portion, reacts 3-10h, and unreacted HCl gases enter pre-reaction after being flowed out from main reaction kettle top portion
In device, reacted at 50-90 DEG C with glycerine；The a small amount of HCl gases discharged by pre-reactor are inhaled by falling-film absorber
It receives.
Reaction product in the pre-reactor, which is sent in main reaction kettle, is further reacted.
The addition of the cerium modified zirconium-silicon molecular sieve catalyst is the 0.05-0.3%, preferably 0.1- of qualities of glycerin
0.2%.
The molar ratio of the HCl and glycerine is 3-10:1, preferably 3-5:1.
The glycerine can be the relatively low glycerine of purity, prepared by the preferably glycerine of 50wt%, especially biodiesel
The by-product glycerol obtained in journey.
The preparation method of the cerium modified zirconium-silicon molecular sieve catalyst, includes the following steps：
In molar ratio 1：Zirconium nitrate and cetyl trimethylammonium bromide (CTAB) are dissolved in deionized water by 0.5-2.
In zirconium silicon than 1:Ethyl orthosilicate is added dropwise in 2-4, and preferably zirconium silicon is than 1:3, aging 6-12h is stirred after being added dropwise；Then ammonium hydroxide is used
PH value is adjusted to 10-12, is stirred after 12-24h, in 100-120 DEG C of crystallization 48-72h, then being filtered in reactant reaction kettle, use
Deionized water is washed to neutrality, is dried after roasting 6-12h at 400-500 DEG C, is obtained mesoporous Zr-Si molecular sieve；
By Ce (NO3)3·6H2O is dissolved in distilled water, adds in mesoporous Zr-Si molecular sieve, then by the use of ammonium hydroxide as precipitating reagent, control
PH value processed is in 10-11；3-12h agings are stirred at 110-140 DEG C；Then it is filtered, washing precipitation；By filter cake in 120-
Dry 5-24h, is placed in Muffle furnace and roasts 6-12h at 350-500 DEG C, obtain cerium modified zirconium-silicon molecular sieve catalyst at 150 DEG C
Finished product.
Because the first step reaction condition of glycerine and HCl are more mild, reaction speed is very fast, using by unreacted HCl gas
The method that body is reacted with glycerine in pre-reactor can rationally utilize the heat of unreacted HCl gases, reduce energy consumption, and can
To shorten the reaction time.
Compared with prior art, the present invention it has the following advantages：Cerium modified zirconium-silicon molecular sieve catalyst system of the present invention
Preparation Method is simple, high catalytic efficiency, and the usage amount of catalyst is few, and catalytic life is longer, and can carry out activating and regenerating use,
Wherein the yield of 1,3-DCP can reach more than 85%, and the conversion ratio of glycerine is 100%；It is relatively low for the purity requirement of glycerine,
Glycerine used in reaction can be the relatively low by-product glycerol of the purity obtained in preparation of biodiesel；The dichlorohydrin of the present invention
Good, the high conversion rate of glycerine of selectivity.
Specific embodiment
Embodiment
Embodiment 1
The preparation of cerium modified zirconium-silicon molecular sieve catalyst
In molar ratio 1：1 is dissolved in zirconium nitrate and cetyl trimethylammonium bromide (CTAB) in deionized water.In zirconium
Silicon is than 1:2 are added dropwise ethyl orthosilicate, and aging 12h is stirred after being added dropwise；Then pH value is adjusted to 11 with ammonium hydroxide, after stirring 12h
, in 120 DEG C of crystallization 48h, then filtering, be washed with deionized to neutrality, dry after at 400 DEG C in reactant reaction kettle
12h is roasted, obtains mesoporous Zr-Si molecular sieve；
By Ce (NO3)3·6H2O is dissolved in distilled water, adds in mesoporous Zr-Si molecular sieve, then by the use of ammonium hydroxide as precipitating reagent, control
PH value processed is 10；6h agings are stirred at 110 DEG C；Then it is filtered, washing precipitation；Filter cake is dried into 12h at 120 DEG C,
It is placed in Muffle furnace and roasts 6h at 400 DEG C, obtain cerium modified zirconium-silicon molecular sieve finished catalyst.
Dichloropropane reaction, reaction time 6h, the receipts at a temperature of differential responses are prepared with above-mentioned catalyst glycerine
Rate is as follows：
| Reaction temperature | Glycerol conversion yield | 2-MCPD yields | 3-MCPD yields | 1,3-DCP yields | 1,3-DCP yields | 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
In molar ratio 1：2 are dissolved in zirconium nitrate and cetyl trimethylammonium bromide (CTAB) in deionized water.In zirconium
Silicon is than 1:4 are added dropwise ethyl orthosilicate, and aging 6h is stirred after being added dropwise；Then pH value is adjusted to 12 with ammonium hydroxide, stir rear handle for 24 hours
In 120 DEG C of crystallization 72h in reactant reaction kettle, then filter, be washed with deionized to neutrality, dry and roasted after at 500 DEG C
12h is burnt, obtains mesoporous Zr-Si molecular sieve；
By Ce (NO3)3·6H2O is dissolved in distilled water, adds in mesoporous Zr-Si molecular sieve, then by the use of ammonium hydroxide as precipitating reagent, control
PH value processed is 11；12h agings are stirred at 140 DEG C；Then it is filtered, washing precipitation；Filter cake is dried into 6h at 150 DEG C,
It is placed in Muffle furnace and roasts 6h at 500 DEG C, obtain cerium modified zirconium-silicon molecular sieve finished catalyst.
Dichloropropane reaction, reaction time 9h, the receipts at a temperature of differential responses are prepared with above-mentioned catalyst glycerine
Rate is as follows：
| Reaction temperature | Glycerol conversion yield | 2-MCPD yields | 3-MCPD yields | 1,3-DCP yields | 1,3-DCP yields | 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 present invention is not limited to the embodiments described above,
Without departing substantially from the present invention substantive content in the case of, those skilled in the art can make it is any it is conspicuously improved, replace
It changes or modification is all within the scope of the present invention.
Claims (9)
1. a kind of method using cerium modified zirconium-silicon molecular sieve catalyst preparation dichlorohydrin includes the following steps：By glycerine with
Cerium modified zirconium-silicon molecular sieve catalyst is placed in main reaction kettle, is heated to 90-125 DEG C, and HCl gases are compressed to be distributed by gas
Device enters main reaction bottom portion, reacts 3-10h, and unreacted HCl gases enter pre-reactor after being flowed out from main reaction kettle top portion
In, it is reacted at 50-90 DEG C with glycerine；The a small amount of HCl gases discharged by pre-reactor are absorbed by falling-film absorber；
Wherein in molar ratio 1：Zirconium nitrate and cetyl trimethylammonium bromide (CTAB) are dissolved in deionized water by 0.5-2,
In zirconium silicon than 1:Ethyl orthosilicate is added dropwise in 2-4, and aging 6-12h is stirred after being added dropwise；Then pH value is adjusted to 10- with ammonium hydroxide
12, it stirs after 12-24h, in 100-120 DEG C of crystallization 48-72h, then filtering, be washed with deionized in reactant reaction kettle
To neutrality, dry after roasting 6-12h at 400-500 DEG C, obtain mesoporous Zr-Si molecular sieve；By Ce (NO3)3·6H2O is dissolved in steaming
In distilled water, mesoporous Zr-Si molecular sieve is added in, then by the use of ammonium hydroxide as precipitating reagent, control ph is in 10-11；It is stirred at 110-140 DEG C
Mix 3-12h agings；Then it is filtered, washing precipitation；Filter cake at 120-150 DEG C is dried into 5-24h, is placed in Muffle furnace
350-500 DEG C of roasting 6-12h, obtains cerium modified zirconium-silicon molecular sieve finished catalyst.
2. the method as described in claim 1, it is characterised in that the reaction product in the pre-reactor is sent to main reaction kettle
In further reacted.
3. the method as described in claim 1, it is characterised in that the addition of the cerium modified zirconium-silicon molecular sieve catalyst is sweet
The 0.05-0.3% of oil quality.
4. method as claimed in claim 3, it is characterised in that the addition of the cerium modified zirconium-silicon molecular sieve catalyst is sweet
The 0.1-0.2% of oil quality.
5. the method as described in claim 1, it is characterised in that the molar ratio of the HCl and glycerine is 3-10:1.
6. method as claimed in claim 5, it is characterised in that the molar ratio of the HCl and glycerine is 3-5:1.
7. method as claimed in claim 5, it is characterised in that the zirconium silicon is than 1:3.
8. the method as described in claim 1, it is characterised in that the glycerine is the purity obtained in preparation of biodiesel
Relatively low by-product glycerol.
9. the method as described in claim 1, it is characterised in that the concentration of the glycerine is more than 50wt%.
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| 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 |
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| 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 |
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| Publication Number | Publication Date |
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| CN106242947A CN106242947A (en) | 2016-12-21 |
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| CN103111326B (en) * | 2013-03-11 | 2016-01-06 | 南京工业大学 | A kind of carboxylic acid group functionalization SBA molecular sieve catalyst of glycerol hydrochlorination synthesizing dichloropropanol |
| CN104151139B (en) * | 2014-07-24 | 2016-04-06 | 江苏大学 | A kind of HY type molecular sieve catalytic glycerin chlorination prepares the method for dichlorohydrine |
| CN104163753B (en) * | 2014-07-24 | 2016-05-25 | 江苏大学 | A kind of modification L-type molecular sieve catalytic glycerin chlorination is prepared the method for dichlorohydrin |
| 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 |
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