CN100430130C - Bimetallic salt catalyst system and its uses - Google Patents
Bimetallic salt catalyst system and its uses Download PDFInfo
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- CN100430130C CN100430130C CNB2006100398673A CN200610039867A CN100430130C CN 100430130 C CN100430130 C CN 100430130C CN B2006100398673 A CNB2006100398673 A CN B2006100398673A CN 200610039867 A CN200610039867 A CN 200610039867A CN 100430130 C CN100430130 C CN 100430130C
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- salt catalyst
- catalyst
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- monoethylene glycol
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- 239000003054 catalyst Substances 0.000 title claims abstract description 55
- 150000003839 salts Chemical class 0.000 title claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 238000009835 boiling Methods 0.000 claims abstract description 6
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- 229910052751 metal Inorganic materials 0.000 claims abstract description 4
- 239000002184 metal Substances 0.000 claims abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 3
- 150000002367 halogens Chemical class 0.000 claims abstract description 3
- 239000001301 oxygen Substances 0.000 claims abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 3
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 52
- 238000006243 chemical reaction Methods 0.000 claims description 49
- 238000006703 hydration reaction Methods 0.000 claims description 21
- 230000036571 hydration Effects 0.000 claims description 19
- 230000035484 reaction time Effects 0.000 claims description 12
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- -1 bicarbonate radical Chemical class 0.000 claims description 4
- 235000011187 glycerol Nutrition 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 125000002091 cationic group Chemical group 0.000 claims description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical class CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 claims description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims 1
- 239000010452 phosphate Substances 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 6
- 239000001257 hydrogen Substances 0.000 abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 abstract description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 abstract description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 150000001450 anions Chemical class 0.000 abstract 2
- 150000001768 cations Chemical class 0.000 abstract 2
- 125000004122 cyclic group Chemical group 0.000 abstract 1
- 229910017604 nitric acid Inorganic materials 0.000 abstract 1
- 150000002910 rare earth metals Chemical class 0.000 abstract 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 37
- 238000000034 method Methods 0.000 description 16
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 12
- 239000000376 reactant Substances 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- 239000002994 raw material Substances 0.000 description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000007172 homogeneous catalysis Methods 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- 229910052719 titanium Inorganic materials 0.000 description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 5
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- 239000003426 co-catalyst Substances 0.000 description 3
- 230000006837 decompression Effects 0.000 description 3
- 238000007210 heterogeneous catalysis Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000010791 quenching Methods 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- QNEFNFIKZWUAEQ-UHFFFAOYSA-N carbonic acid;potassium Chemical compound [K].OC(O)=O QNEFNFIKZWUAEQ-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 229910000420 cerium oxide Inorganic materials 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 230000007096 poisonous effect Effects 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- WJEIYVAPNMUNIU-UHFFFAOYSA-N [Na].OC(O)=O Chemical compound [Na].OC(O)=O WJEIYVAPNMUNIU-UHFFFAOYSA-N 0.000 description 1
- 239000003957 anion exchange resin Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000011964 heteropoly acid Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The present invention discloses a bimetal salt catalyst system and an application thereof. The system is composed of the following bimetal salt catalyst NM and solvent NS for dissolving the bimetal salt catalyst. The specific substances of the bimetal salt catalyst system have the following general formula: NM (NY (I) +MO (II)) +NS (III), wherein N is one or various kinds of the cations of the metal of the IA and IIA main groups or the metal of the IB and IIB subgroups, and Y is one or a various kinds of the anions of halogen, a carbonic acid (hydrogen) radical, a sulfuric acid (hydrogen) radical or a phosphoric acid (hydrogen) radical in an NM bimetal salt catalyst (I) formula. M is one or various kinds of the cations of rare earth metal, and O is one or various kinds of the anions of oxygen, a carbonic acid radical or a nitric acid radical in the (II) formula. The NS solvent is organic solvent or water, and has a boiling point higher than 190 DEG C for dissolving the bimetal salt catalyst NM. The catalyst system has the advantages of high activity, high selectivity and good cyclic use performance.
Description
Technical field
The present invention relates to a kind of catalyst system and application thereof, be equipped with the bimetallic salt catalyst system and the application thereof of monoethylene glycol more specifically to a kind of hydration legal system.
Background technology
Monoethylene glycol (Monoethylene Glycol, abbreviated as MEG), claim glycol again, or ethylene glycol, it is a kind of important Organic Chemicals, after being found and terephthalic acid (TPA) (PTA) reaction generation PET, can be used as the raw material of polyester fiber and polyester plastics, the consumption of monoethylene glycol increases sharply.The synthetic method of monoethylene glycol is generally oxirane direct hydration method and catalytic hydration, at present to make water and oxirane mol ratio (be called for short water than) be 22～25: 1 raw material to the direct hydration method technology that adopts of industrial production monoethylene glycol, total yield of products is 89%～90%, device need be provided with a plurality of evaporimeters, consume lot of energy and be used for dehydration, cause that the technological process of production is long, equipment is many, energy consumption is high, directly influence the production cost of monoethylene glycol, and amount of industrial wastewater is big.Catalytic hydration is that recently both at home and abroad experts and scholars and business circles think and cut down the consumption of raw materials and the effective method of energy consumption that it can be divided into the indirect hydration method of heterogeneous catalysis hydration method, homogeneous catalysis direct hydration method and homogeneous catalysis again.Patents more both domestic and external as: JP57-139026, WO97/33850, RU2002726, US4760200, CN1282310A etc. disclose heterogeneous catalysis hydration legal system and have been equipped with monoethylene glycol, the typical heterogeneous catalysis that is adopted is the anion exchange resin that contains molybdate, carbonate, halide ion acid, this method has the advantage that does not need separating catalyst, but all there are problems such as resin swelling, active constituent loss more or less in such catalyst.The indirect hydration method of homogeneous catalysis claims the ethylene carbonate method again, i.e. oxirane elder generation and CO under the effect of catalyst
2Effect generates ethylene carbonate, ethylene carbonate adds water and resolves into monoethylene glycol under the effect of catalyst then, patents more both domestic and external as: GB2098985A, JP57-106631, US4400559, US4508972, US5138073, US6080897, CN1068865C etc. all disclose the indirect hydration legal system of homogeneous catalysis and have been equipped with monoethylene glycol, but this method must have CO
2Condition under carry out the higher and two-step process relative complex of pressure.The homogeneous catalysis direct hydration method is that oxirane (EO) and water are made into mixed aqueous solution in proportion, in reactor, carry out the prepared in reaction monoethylene glycol, some patents as: WO85/04406, GB2083026A, US4967018 etc. disclose the method, the catalyst that uses is organometallic complex, as: [(Ph
3P)
2W] VO
3, [(Ph
3P)
2N] WO
3, (PPN)
2MoO
4, (PPM)
2MoO
4Deng, these catalyst all have certain toxicity, and the auxiliary agent that adds is as C
6H
5CH
3, C
2H
2Cl
2, C
6H
6Big, inflammable poisonous Deng consumption.The application of Chinese patent publication number CN1237481A discloses the complex catalyst of a kind of inorganic salts and heteropolyacid salt, the mol ratio of oxirane and water can drop to 4: 1,100～150 ℃ of reaction temperatures, 8～30 minutes reaction time, the EO conversion ratio reaches 95.0～99.9%, and the MEG selectivity has only 88～96%; The application of Chinese patent publication number CN1565735A, CN1566049A, CN1618514A, series of patents such as CN1589969A, CN1611475A recently discloses the catalyst of a kind of solid acid and salt of weak acid, the mol ratio of oxirane and water can drop to below 10: 1,150 ℃ of reaction temperatures, 10～30 minutes reaction time, the EO conversion ratio reaches 100%, the MEG selectivity has only 89～92%, and visible selectivity is still waiting further raising, and its catalyst can not recycle.
Summary of the invention
The objective of the invention is to have in order to solve in the prior art catalyst that resin swelling, active constituent run off, catalyst is poisonous or must CO arranged
2Condition under react, pressure is higher and the selectivity of two-step process relative complex and EG is lower problem, provide a kind of make oxirane and one step of water directly effect generate high reaction activity and the high monoethylene glycol selectivity and the smaller bimetallic salt catalyst system of water of monoethylene glycol.
Another object of the present invention provides above-mentioned caltalyst and ties up to the hydration legal system and be equipped with application in the monoethylene glycol.
Technical scheme of the present invention is as follows:
A kind of bimetallic salt catalyst system, this system is made up of the solvent NS of following bimetallic salt catalyst NM and dissolving bimetallic salt catalyst; The general formula that concrete material is formed is:
NM〔NY(I)+MO(II)〕+NS(III)
In NM bimetallic salt catalyst (I) formula: N be IA, IIA main group metal cationic one or more;
Y be halogen, carbonic acid (hydrogen) root, sulfuric acid (hydrogen) root or phosphoric acid (hydrogen) root anionic one or more;
(II) in the formula: M be rare earth metal cationic one or more;
O is one or more of oxygen, carbonate, nitrate anion;
The NS solvent is the boiling point of dissolving NM bimetallic salt catalyst organic solvent and/or the water greater than 190 ℃.
Described catalyst system, its formula of (I) is 10～1000: 1 with both weight ratios of general formula (II), general formula (I) is 0.01～1: 1 with both weight ratios of general formula (III).
Described catalyst system, wherein N is Li
+, Na
+, K
+, Ca
2+, Mg
2+Or Sr
2+Y is Br
-, I
-, Cl
-, CO
3 2-, HCO
3 -, HSO
4 -Or PO
4 3-M is La
3+, La
+, Ce
4+, Ce
3+Or Ce
+O is O
2-, CO
3 2-Or NO
3 -Boiling point is monoethylene glycol, propane diols, glycerine, diethylene glycol (DEG), triethylene glycol, carbonic ester or polyethers greater than 190 ℃ organic solvent.
Described catalyst system and catalyzing is equipped with application in the monoethylene glycol in the hydration legal system.The condition of its application for this caltalyst tie up to the hydration legal system when being equipped with monoethylene glycol the water ratio be 1～10: 1, hydration reaction is carried out in intermittently tank reactor or continuous tubular reactor, reaction pressure is 0.1～10MPa, and reaction temperature is 45～200 ℃, and the reaction time is 1～30 minute;
Described application, wherein reaction pressure is 0.5～3MPa, and reaction temperature is 60～150 ℃, and the reaction time is 5～10 minutes.
Beneficial effect of the present invention:
Catalyst system activity of the present invention is high, selectivity is high, it is good to recycle performance.Caltalyst of the present invention ties up to the hydration legal system when being equipped with monoethylene glycol, the oxirane conversion ratio can reach 100%, the monoethylene glycol selectivity can reach more than 99%, and caltalyst of the present invention ties up to when recycling, replace the circulation monoethylene glycol with non-monoethylene glycol high boiling solvent, solved low water than circulation monoethylene glycol under the condition to the difficulty of selectivity significant impact, this just makes at low water than the high selectivity of bonding ethylene glycol still under the condition.Even the raw materials components mole ratio of water and oxirane reduces at 1.5: 1 o'clock, the monoethylene glycol selectivity still can reach (as embodiment 4) more than 97%, and the higher selectivity (as comparative example 3) of bonding ethylene glycol still when adopting monoethylene glycol to make solvent also to make water relatively lower.This catalyst system safety, nontoxic is used simply, and industrial wastewater is few, and production cost is low, and the industrialization of homogeneous catalysis direct hydration method manufacture order ethylene glycol is had great breakthrough.
The specific embodiment
The present invention is further described below in conjunction with specific embodiment.
Embodiment 1
Add entry 400 grams, sodium carbonate 30 grams, lanthana 0.6 gram in 1000 milliliters of titanium material autoclaves, 100 gram oxirane are by electronic balance metering passing through N
2Or CO
2Be pressed in the above autoclave, electrical heating control reaction temperature is 120 ℃, and reaction pressure is 1.0MPa, 20 minutes reaction time, stop reaction, and the conversion ratio of reactant liquor cooling back sample analysis oxirane is 100%, the selectivity of monoethylene glycol is 99.08%.
Embodiment 2
Add entry 400 grams, KBr 30 grams, cerium oxide 0.6 gram in 1000 milliliters of titanium material autoclaves, 100 gram oxirane are by electronic balance metering passing through N
2Or CO
2Be pressed in the above autoclave, electrical heating control reaction temperature is 120 ℃, and reaction pressure is 1.0MPa, 20 minutes reaction time, stop reaction, and the conversion ratio of reactant liquor cooling back sample analysis oxirane is 100%, the selectivity of monoethylene glycol is 99.28%.
Comparative example 1
Add entry 400 grams in 1000 milliliters of titanium material autoclaves, 100 gram oxirane are by electronic balance metering passing through N
2Be pressed in the above autoclave, electrical heating control reaction temperature is 120 ℃, and reaction pressure is 1.0MPa, 30 minutes reaction time, stop reaction, and the conversion ratio of reactant liquor cooling back sample analysis oxirane is 99.20%, the selectivity of monoethylene glycol is 81.20%.
Embodiment 3
Take by weighing catalyst carbonic acid potassium 300 grams, co-catalyst lanthana 6 grams, be dissolved in the 4000 gram water, the aqueous catalyst solution and the measuring container of preparation place on the electronic scale together, the steel cylinder that oxirane is housed is placed on another electronic scale, with two measuring pumps respectively with aqueous catalyst solution and oxirane continuously to the tubular reactor feeding of ￠ 25 * 3 * 600, tubular reactor places electric furnace, the control reaction temperature is 100～120 ℃, reaction pressure is 1.0MPa, the inlet amount of regulating measuring pump control aqueous catalyst solution is 1.28Kg/hr, the inlet amount of oxirane is 0.32Kg/hr, the raw materials components mole ratio that is water and oxirane is 10: 1, reactant liquor is used water quench after the pressure-reducing valve decompression, the conversion ratio of sample analysis oxirane is 100%, and the selectivity of monoethylene glycol is greater than 99.50%.
Embodiment 4
Add entry 63 grams, glycerine 200 grams, sodium carbonate 30 grams, lanthana 1.0 grams in 1000 milliliters of titanium material autoclaves, 100 gram oxirane are by electronic balance metering passing through N
2Or CO
2Be pressed in the above autoclave, electrical heating control reaction temperature is 120 ℃, and reaction pressure is 1.0MPa, 20 minutes reaction time, stop reaction, and the conversion ratio of reactant liquor cooling back sample analysis oxirane is 100%, the selectivity of monoethylene glycol is 97.11%.
Embodiment 5
Add entry 145 grams, ethylene carbonate 250 grams, sodium carbonate 30 grams, lanthana 0.3 gram in 1000 milliliters of titanium material autoclaves, 100 gram oxirane are by electronic balance metering passing through N
2Or CO
2Be pressed in the above autoclave, electrical heating control reaction temperature is 120 ℃, and reaction pressure is 1.0MPa, 20 minutes reaction time, stop reaction, and the conversion ratio of reactant liquor cooling back sample analysis oxirane is 100%, the selectivity of monoethylene glycol is 99.26%.
Comparative example 2
Add entry 280 grams, monoethylene glycol 50 grams, sodium carbonate 30 grams, lanthana 1.0 grams in 1000 milliliters of titanium material autoclaves, 100 gram oxirane are by electronic balance metering passing through N
2Or CO
2Be pressed in the above autoclave, electrical heating control reaction temperature is 120 ℃, and reaction pressure is 1.0MPa, 30 minutes reaction time, stop reaction, and the conversion ratio of reactant liquor cooling back sample analysis oxirane is 100%, the selectivity of monoethylene glycol is 92.21%.
Embodiment 6 (dynamic circulation)
Take by weighing catalyst carbonic acid sodium 300 grams, co-catalyst cerium oxide 10 grams, be dissolved in 1000 gram water and the 3000 gram glycerine, catalyst alcohol solution and measuring container preparation or that reclaim place on the electronic scale together, the steel cylinder that oxirane is housed is placed on another electronic scale, with two measuring pumps respectively with aqueous catalyst solution and oxirane continuously to the tubular reactor feeding of ￠ 25 * 3 * 600, tubular reactor places electric furnace, the control reaction temperature is 100～120 ℃, reaction pressure is 1.0MPa, the inlet amount of regulating measuring pump control aqueous catalyst solution is 1.28Kg/hr, the inlet amount of oxirane is 0.32Kg/hr, the raw materials components mole ratio that is water and oxirane is 2.4: 1, reactant liquor is used water quench after the pressure-reducing valve decompression, the conversion ratio of sample analysis oxirane is 100%, and the selectivity of monoethylene glycol is greater than 98.0%.Reactant liquor reclaims catalyst circulation and uses.
Comparative example 3
Take by weighing catalyst carbonic acid potassium 300 grams, co-catalyst lanthana 10 grams, be dissolved in 1000 gram water and the 3000 gram monoethylene glycols, the catalyst alcohol solution and the measuring container of preparation place on the electronic scale together, the steel cylinder that oxirane is housed is placed on another electronic scale, with two measuring pumps respectively with aqueous catalyst solution and oxirane continuously to the tubular reactor feeding of ￠ 25 * 3 * 600, tubular reactor places electric furnace, the control reaction temperature is 100～120 ℃, reaction pressure is 1.0MPa, the inlet amount of regulating measuring pump control aqueous catalyst solution is 1.28Kg/hr, the inlet amount of oxirane is 0.32Kg/hr, the raw materials components mole ratio that is water and oxirane is 2.4: 1, reactant liquor is used water quench after the pressure-reducing valve decompression, the conversion ratio of sample analysis oxirane is 100%, and the selectivity of monoethylene glycol is greater than 83.38%.
Claims (6)
1, a kind of bimetallic salt catalyst system, it is characterized in that this system by following bimetallic salt catalyst NM and the dissolving bimetallic salt catalyst solvent NS form; The general formula that concrete material is formed is:
NM〔NY(I)+MO(II)〕+NS(III)
Wherein:
In NM bimetallic salt catalyst (I) formula: N be IA, IIA main group metal cationic one or more; Y is one or more of halogen, carbonate, bicarbonate radical, bisulfate ion or phosphate radical anion; (II) in the formula: M be rare earth metal cationic one or more; O is one or more of oxygen, carbonate or nitrate anion;
The NS solvent is the boiling point of dissolving NM bimetallic salt catalyst organic solvent and/or the water greater than 190 ℃.
2, catalyst system according to claim 1 is characterized in that general formula (I) and both weight ratios of general formula (II) are 10～1000: 1, and general formula (I) is 0.01～1: 1 with both weight ratios of general formula (III).
3, catalyst system according to claim 1 is characterized in that N is Li
+, Na
+, K
+, Ca
2+, Mg
2+, or Sr
2+Y is Br
-, I
-, Cl
-, CO
3 2-, HCO
3 -, HSO
4 -Or PO
4 3-M is La
3+, La
+, Ce
4+, Ce
3+Or Ce
+O is O
2-, CO
3 2-Or NO
3 -Boiling point is monoethylene glycol, propane diols, glycerine, diethylene glycol (DEG), triethylene glycol, carbonic ester or polyethers greater than 190 ℃ organic solvent.
4, the described catalyst system and catalyzing of claim 1 is equipped with application in the monoethylene glycol in the hydration legal system.
5, application according to claim 4, it is characterized in that the condition that this catalyst system is used is 1～10: 1 for water ratio when the hydration legal system is equipped with monoethylene glycol, hydration reaction is carried out in intermittently tank reactor or continuous tubular reactor, reaction pressure is 0.1～10MPa, reaction temperature is 45～200 ℃, and the reaction time is 1～30 minute.
6, application according to claim 5 is characterized in that reaction pressure is 0.5～3MPa, and reaction temperature is 60～150 ℃, and the reaction time is 5～10 minutes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100398673A CN100430130C (en) | 2006-04-25 | 2006-04-25 | Bimetallic salt catalyst system and its uses |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100398673A CN100430130C (en) | 2006-04-25 | 2006-04-25 | Bimetallic salt catalyst system and its uses |
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| Publication Number | Publication Date |
|---|---|
| CN1836774A CN1836774A (en) | 2006-09-27 |
| CN100430130C true CN100430130C (en) | 2008-11-05 |
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ID=37014365
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006100398673A Expired - Fee Related CN100430130C (en) | 2006-04-25 | 2006-04-25 | Bimetallic salt catalyst system and its uses |
Country Status (1)
| Country | Link |
|---|---|
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1278236A (en) * | 1997-10-30 | 2000-12-27 | 国际壳牌研究有限公司 | Catalytic hydrolysis of alkylene oxides |
-
2006
- 2006-04-25 CN CNB2006100398673A patent/CN100430130C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1278236A (en) * | 1997-10-30 | 2000-12-27 | 国际壳牌研究有限公司 | Catalytic hydrolysis of alkylene oxides |
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| Publication number | Publication date |
|---|---|
| CN1836774A (en) | 2006-09-27 |
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