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CN103143382B - Catalyst for synthesizing methyl tertiary butyl ether (MTBE) and methyl isoamyl ether, and preparation method - Google Patents

Catalyst for synthesizing methyl tertiary butyl ether (MTBE) and methyl isoamyl ether, and preparation method Download PDF

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Publication number
CN103143382B
CN103143382B CN201310079578.6A CN201310079578A CN103143382B CN 103143382 B CN103143382 B CN 103143382B CN 201310079578 A CN201310079578 A CN 201310079578A CN 103143382 B CN103143382 B CN 103143382B
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catalyst
molecular sieve
hour
methyl
bonding agent
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CN103143382A (en
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张宇
刘二明
苗晓涛
刘述全
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Tianjin Nantian New Material Research Center Co Ltd
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Tianjin Nantian New Material Research Center Co Ltd
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
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Abstract

The invention relates to a catalyst for synthesizing methyl tertiary butyl ether (MTBE) and methyl isoamyl ether, and a preparation method. The catalyst comprises a molecular sieve and a bonding agent, wherein the bonding agent takes up 10-20% of the catalyst in mass, the bonding agent is mixed glue solution of nanometer aluminum oxide and water glass, the water glass takes up 60-95% of the bonding agent, and the mole ratio of SiO2/Al2O3 in the molecular sieve is 25-500, the bonding agent used for forming is silicon-aluminum mixed glue solution containing 60-95% of water glass. The formed catalyst uses the low-concentration hydrochloric acid for removing aluminum. According to the catalyst, under the reaction temperature of 85 DEG C and 0MPa, the conversion rate of isobutene can achieve 55-60%, and the conversion rate of C5 iso-olfin can achieve 35-40%; and under the reaction temperature of 85 DEG C and 8MPa, the conversion rate of isobutene can achieve 90-5-60%, and the conversion rate of C5 iso-olfin can achieve 60-65%. The catalyst can be repeatedly regenerated without secondary pollution.

Description

The catalyst of synthesize methyl tert-butyl ether and methyl isoamyl ether and preparation method
Technical field
The present invention relates to catalyst and the preparation method of a kind of synthesize methyl tert-butyl ether and methyl isoamyl ether, specifically by carbon four and carbon five isomeric olefines, produced catalyst and the preparation method of methyl tertiary butyl ether(MTBE) and methyl isoamyl ether.
Background technology
Methyl tertiary butyl ether(MTBE) (MTBE) has very high clear octane number, can dissolve each other preferably with gasoline, for gasoline alkylate, direct steaming gasoline, catalytically cracked gasoline etc., has good mediation effect.As gasoline additive, at society, have in occupation of critical role.It can not only effectively improve octane number and efficiency of combustion, reduce its cost, can also improve automotive performance, and it is not leaded in the tail gas of discharge, CO discharge capacity has also reduced 30%, also reduced the discharge of other harmful substances such as benzene, butadiene, ozone simultaneously, reduced the impact of vehicle exhaust on health, this is that general ethers does not have advantages of.
Generally there is temperature and the shorter problem of catalyst life in the catalyst of synthesize methyl tert-butyl ether and methyl isoamyl ether at present, Chinese patent CN101773848A discloses compound rare earth oxide molecular sieve, take Hydrogen beta-molecular sieve as carrier, use infusion process to mix rare earth oxide and carry out sour modification and make compound rare earth oxide molecular sieve catalyst.The rare earth element of large quantity is grown and used to this compound rare earth oxide molecular sieve catalyst generated time, and cost is higher.
Summary of the invention
The catalyst and the preparation method that the object of this invention is to provide a kind of synthesize methyl tert-butyl ether and methyl isoamyl ether, can overcome the defect of prior art, the catalyst serviceability temperature and the shorter problem of catalyst life that particularly exist.The evident characteristic of producing the catalyst of methyl tertiary butyl ether(MTBE) and methyl isoamyl ether by carbon four and carbon five isomeric olefines of the present invention is to have improved serviceability temperature and pressure, and solved the shortcoming of easily being dissolved by carbon five when catalyst temperature is higher, extended the reaction life-span of catalyst.Catalyst non-secondary pollution after simultaneously using, its composition is consistent with soil, can be buried also can be as construction material, and the catalyst using is at present the macromolecular material containing a large amount of sulphur, dead catalyst can only burn, and can produce a large amount of sulfur dioxide pollution air.The feature of this catalyst is directly to use the molecular sieve plastic Kaolinite Preparation of Catalyst containing mother liquor, greatly reduced the use of perforating agent, and aperture is even, duct is unobstructed.
The catalyst of synthesize methyl tert-butyl ether provided by the invention and methyl isoamyl ether comprises molecular sieve and adhesive, adhesive accounts for 10 ~ 20% of catalyst quality, wherein adhesive is the mixed glue solution of nano aluminium oxide and waterglass, and waterglass accounts for 60 ~ 95% of adhesive.
Described molecular sieve is to use silica gel, sodium metaaluminate, the thin water aluminium of plan and sheet alkali as raw material, controls SiO 2: Al 2o 3: Na 2o:H 2o=1:(0.002 ~ 0.04): (0.03 ~ 0.05): (8 ~ 15), synthesis condition: 80 ~ 160 ℃ of temperature, pressure 5 ~ 15Mpa, time 24-72 hour.SiO in described molecular sieve 2/ Al 2o 3mol ratio is 25 ~ 500.
The step that the preparation method of the catalyst by carbon four and carbon five isomeric olefine synthesize methyl tert-butyl ethers and methyl isoamyl ether provided by the invention comprises is as follows:
1) by metering, the molecular sieve containing mother liquor is evenly mixed with Alusil bonding agent, at 40 ~ 90 ℃, stir 0.5 ~ 1 hour, with 20% sulfuric acid, regulate PH=7 ~ 8, after stirring, filter;
2) filter cake keeps 0.5 ~ 1 hour at 60-80 ℃ with aqueous ammonium chloride solution, exchanges 1 ~ 4 time, filters, and washes 1 ~ 4 time, is hydrogen type molecular sieve colloid; After hydrogen type molecular sieve roasting, specific area is 400 ~ 700m 2/ g.
3) add shaping assistant (for example high molecular polymer shaping assistant) and water again, stir, filter, 100 ~ 130 ℃ are dried 1 ~ 5 hour, extruded moulding.
4) 100 ~ 130 ℃ dry 1 ~ 5 hour, 400 ~ 600 ℃ of roastings 3 ~ 8 hours, are NDC catalyst.
5) immerse in aqueous hydrochloric acid solution, dealuminzation 1 ~ 4h at 50 ~ 80 ℃, washes 1-2 time, at 100 ~ 130 ℃, is dried 1 ~ 5 hour, is NDC-1 catalyst.
NDC-1 catalyst is the Dealumination catalyst of NDC, and two kinds of catalyst all can be for reaction of the present invention.
The molecular sieve containing mother liquor described in step 1), its molecular sieve solid quality accounts for 25 ~ 45% of gross mass.
Shaping assistant described in step 3) is calcium polyacrylate (CPA), and auxiliary agent can be removed through high-temperature roasting.Shaping assistant is 5% ~ 20% of molecular sieve quality, to improve catalyst strength.。
The concentration of the aqueous hydrochloric acid solution described in step 5) is 0.5 ~ 2mol/L.
Carbon four in the present invention and carbon five isomeric olefines are produced the evaluating catalyst condition of methyl tertiary butyl ether(MTBE) and methyl isoamyl ether: pack described catalyst into fixed bed, beds ratio of height to diameter is 4 ~ 8, take carbon four, carbon five isomeric olefines is unstripped gas, the independent charging of methyl alcohol, controlling reaction temperature is 65 ~ 120 ℃, air speed 0.2 ~ 2.5h -1, reaction pressure 0 ~ 10MPa, the mol ratio of methyl alcohol and unstripped gas is 1.3 ~ 5.
It is long entire life that described carbon four and carbon five isomeric olefines are produced the catalyst regeneration of methyl tertiary butyl ether(MTBE) and methyl isoamyl ether, and renovation process is simple, only needs high-temperature roasting to remove carbon deposition removal.
The evident characteristic of the catalyst of synthesize methyl tert-butyl ether provided by the invention and methyl isoamyl ether (NDC) is directly to use the molecular sieve plastic Kaolinite Preparation of Catalyst containing mother liquor, greatly reduced the use of perforating agent, and aperture is even, duct is unobstructed.Improve serviceability temperature and pressure, and solved the shortcoming of easily being dissolved by carbon five when catalyst temperature is higher, extended the reaction life-span of catalyst.The present invention is 85 ℃ of reaction temperatures, and under 0Mpa, isobutene conversion reaches 55 ~ 60%, and carbon five isomeric olefine conversion ratios reach 35 ~ 40%; 85 ℃ of reaction temperatures, under 8Mpa, isobutene conversion reaches 90 ~ 95%, and carbon five isomeric olefine conversion ratios reach 60 ~ 65%.This catalyst can repeated regeneration, catalyst non-secondary pollution after simultaneously using, its composition is consistent with soil, can be buried also can be as construction material, and the catalyst using is at present the macromolecular material containing a large amount of sulphur, dead catalyst can only burn, and can produce a large amount of sulfur dioxide pollution air.
The catalyst Precursors that the present invention adopts has the features such as high-ratio surface and production environmental protection, and preparation and the modification of its catalyst are simple, go for higher reaction temperature and longer service life, and regeneration condition is simple.
The specific embodiment
The present invention describes in detail in conjunction with specific embodiments.
Embodiment 1
Preparation contains the molecular sieve of mother liquor: silica gel, sodium metaaluminate, the thin water aluminium of plan and sheet alkali are placed in reactor, and control molar ratio is SiO 2: Al 2o 3: Na 2o:H 2o=1:(0.002 ~ 0.04): (0.03 ~ 0.05): (8 ~ 15), be fully uniformly mixed, 80 ~ 160 ℃ of synthesis temperatures, synthesis pressure 5 ~ 15Mpa, reacts 72 hours, cooling, blowing from autoclave, is the molecular sieve (SiO containing mother liquor of the present invention 2/ Al 2o 3mol ratio is 25 ~ 500).In this mother liquor, also contain a large amount of sodium and a small amount of silicon and aluminium.
1) the sieve sample analysis butt number (mass percent that contains molecular sieve solid in unit mass sample) of getting containing mother liquor is 35.6%, gets the waterglass sample analysis SiO that configuration adhesive is used 2concentration.
2) take 857g containing the molecular sieve of mother liquor, and calculate solid molecular sieves quality according to butt number.
3) by solid molecular sieves Mass Calculation, go out SiO 2consumption and nano aluminium oxide consumption, then calculate waterglass consumption by the concentration of sodium silicate analyzing, operate as follows: take 384g waterglass, 15g nano aluminium oxide, put into beaker and stir evenly, this is Alusil bonding agent.
4) 857g is put into container containing the molecular sieve of mother liquor, under agitation adds 3) sial glue, then add 600ml water, then at 60 ℃, stir 1 hour.
5) slowly drip 20% sulfuric acid, regulate PH=7 ~ 8, stirring 1 hour, filter.
6) preparation 1mol/L aqueous ammonium chloride solution 2L, puts into solution by the filter cake of step 5), stirs evenly and is warming up to 80 ℃ and keep 1 hour, filters, and exchanges altogether three times.
7) filter cake of step 6) is put into 2L distilled water, stirring and being warming up to 80 ℃ keeps one hour, filters, and washes altogether twice.
8) filter cake of step 7) is put into 2L distilled water, after stirring, add 45g calcium polyacrylate (CPA) (molecular weight 2,500,000 ~ 3,000,000), stir rear filtration, at 120 ℃, dry.
9) take out the colloid after drying, pulverize, extruded moulding, 120 ℃ of oven dry, 600 ℃ of roastings, are and are denoted as NDC catalyst.
10) the NDC catalyst after roasting is used the hydrochloric acid of 1mol/L at 70 ℃, to carry out dealuminzation, filters after washing twice, at 120 ℃, dries, and is NDC-1 catalyst.NDC-1 catalyst is the Dealumination catalyst of NDC, and two kinds of catalyst all can be for reaction of the present invention.
Embodiment 2
According to example 1 method Kaolinite Preparation of Catalyst, wherein the 3rd) the nano aluminium oxide use amount in step changes 21g into, this catalyst called after NDC-2.
Embodiment 3
According to example 1 method Kaolinite Preparation of Catalyst, wherein the 3rd) the nano aluminium oxide use amount in step changes 6g into, this catalyst called after NDC-3.
Embodiment 4
According to example 1 method Kaolinite Preparation of Catalyst, wherein the 10th) concentration of hydrochloric acid in step changes 2mol/L into, this catalyst called after NDC-4.
Choose above-mentioned four examples and prepare the molecular sieve evaluation of gained, reaction condition: pack described catalyst into fixed bed reactors, beds ratio of height to diameter is 5, take carbon four, carbon five isomeric olefines is unstripped gas, the independent charging of methyl alcohol, and controlling reaction temperature is 85 ℃; Air speed 0.2h -1, reaction pressure is respectively 0Mpa and 8MPa, and the mol ratio of methyl alcohol and unstripped gas is 4, and reaction result is as shown in Table 1.
Table one

Claims (9)

1. a catalyst for synthesize methyl tert-butyl ether and methyl isoamyl ether, it is made by molecular sieve and adhesive, the SiO in molecular sieve 2/ Al 2o 3mol ratio is 25 ~ 500, it is characterized in that:
Described adhesive accounts for 10 ~ 20% of catalyst quality, and wherein adhesive is the mixed glue solution of nano aluminium oxide and waterglass, and waterglass accounts for 60 ~ 95% of adhesive; Preparation method comprises following step:
1) by metering, the molecular sieve containing mother liquor is evenly mixed with Alusil bonding agent, at 40 ~ 90 ℃, stir 0.5 ~ 1 hour, with sulfuric acid, regulate PH=7 ~ 8, after stirring, filter;
2) filter cake keeps exchanging 1 ~ 4 time under 0.5 ~ 1 hour at 60-80 ℃ with aqueous ammonium chloride solution, filters, and washes 1 ~ 4 time, is hydrogen type molecular sieve colloid;
3) add high molecular polymer shaping assistant and water again, stir, filter, filter cake is dried 1 ~ 5 hour, extruded moulding at 100 ~ 130 ℃;
4) 100 ~ 130 ℃ dry 1 ~ 5 hour, 400 ~ 600 ℃ of roastings 3 ~ 8 hours;
5) product that step 4) obtains immerses in aqueous hydrochloric acid solution, and dealuminzation 1 ~ 4h at 50 ~ 80 ℃, washes 1-2 time, and 100 ~ 130 ℃ are dried 1 ~ 5 hour.
2. catalyst according to claim 1, is characterized in that described molecular sieve is to use silica gel, sodium metaaluminate, the thin water aluminium of plan and sheet alkali as raw material, controls mol ratio: SiO 2: Al 2o 3: Na 2o:H 2o=1:0.002 ~ 0.04:0.03 ~ 0.05:8 ~ 15, synthesis condition: 80 ~ 160 ℃ of temperature, pressure 5 ~ 15MPa, time 24-72 hour.
3. the preparation method of the catalyst of synthesize methyl tert-butyl ether claimed in claim 1 and methyl isoamyl ether, is characterized in that comprising following step:
1) by metering, the molecular sieve containing mother liquor is evenly mixed with Alusil bonding agent, at 40 ~ 90 ℃, stir 0.5 ~ 1 hour, with sulfuric acid, regulate PH=7 ~ 8, after stirring, filter;
2) filter cake keeps exchanging 1 ~ 4 time under 0.5 ~ 1 hour at 60-80 ℃ with aqueous ammonium chloride solution, filters, and washes 1 ~ 4 time, is hydrogen type molecular sieve colloid;
3) add high molecular polymer shaping assistant and water again, stir, filter, filter cake is dried 1 ~ 5 hour, extruded moulding at 100 ~ 130 ℃;
4) 100 ~ 130 ℃ dry 1 ~ 5 hour, 400 ~ 600 ℃ of roastings 3 ~ 8 hours;
5) product that step 4) obtains immerses in aqueous hydrochloric acid solution, and dealuminzation 1 ~ 4h at 50 ~ 80 ℃, washes 1-2 time, and 100 ~ 130 ℃ are dried 1 ~ 5 hour.
4. method according to claim 3, is characterized in that the molecular sieve containing mother liquor described in step 1), and its molecular sieve solid quality accounts for 25 ~ 45% of gross mass.
5. method according to claim 3, is characterized in that the shaping assistant described in step 3) is calcium polyacrylate (CPA).
6. method according to claim 3, is characterized in that described shaping assistant is 5% ~ 20% of molecular sieve quality.
7. method according to claim 3, is characterized in that the concentration of the aqueous hydrochloric acid solution described in step 5) is 0.5 ~ 2mol/L.
8. method according to claim 3, is characterized in that the mass concentration of described sulfuric acid is 20%.
9. the application process of the catalyst of a synthesize methyl tert-butyl ether claimed in claim 1 and methyl isoamyl ether, it is characterized in that packing described catalyst into fixed bed, beds ratio of height to diameter is 4 ~ 8, take carbon four, carbon five isomeric olefines is unstripped gas, the independent charging of methyl alcohol, controlling reaction temperature is 65 ~ 120 ℃, air speed 0.2 ~ 2.5h -1, reaction pressure 0 ~ 10MPa, the mol ratio of methyl alcohol and unstripped gas is 1.3 ~ 5.
CN201310079578.6A 2013-03-13 2013-03-13 Catalyst for synthesizing methyl tertiary butyl ether (MTBE) and methyl isoamyl ether, and preparation method Expired - Fee Related CN103143382B (en)

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US5387722A (en) * 1993-09-23 1995-02-07 Texaco Chemical Inc. One-step synthesis of methyl t-butyl ether from t-butanol using pentasil zeolite catalysts
CN101773848B (en) * 2010-01-14 2012-07-11 华东理工大学 Catalyst and preparation method for synthesizing methyl tert-butyl ether

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