CN101550051A - Process for preparing arene selectivity by enhancing methanol aromatizatian and process for preparation of catalyst thereof - Google Patents
Process for preparing arene selectivity by enhancing methanol aromatizatian and process for preparation of catalyst thereof Download PDFInfo
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- CN101550051A CN101550051A CNA2009101356436A CN200910135643A CN101550051A CN 101550051 A CN101550051 A CN 101550051A CN A2009101356436 A CNA2009101356436 A CN A2009101356436A CN 200910135643 A CN200910135643 A CN 200910135643A CN 101550051 A CN101550051 A CN 101550051A
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Abstract
The invention relates to a process for preparing arene selectivity by enhancing methanol aromatizatian. The process uses methanol as raw material, compositely modifies HZSM-5 molecular sieve catalyst by active ions like Ga, Zn, Cu, Cr and Ag for catalyzing methanol aromatizatian, employs the fixed bed continuous process or the floating bed continuous process, wherein the reaction pressure is 0.1-3.5MPa; the reaction temperature is 380-500 DEG C; the space velocity of raw material liquid is 0.1-10.0 h<-1>; and N2 space velocity is 120-800 h<-1>. The advantages of the invention lie in collocation combination of mixing ion modification, and arene selectivity reaches to 70%.
Description
Technical field
The present invention relates to a kind of technology and Preparation of catalysts method thereof that aromatization of methanol is produced arenes selectivity that improve.
Background technology
Aromatic hydrocarbons is a kind of strategic goods and materials, is the raw material of medicine, agricultural chemicals, dyestuff, organic materials and basic chemical industry.Contain the aromatic hydrocarbons elementary cell in medical agricultural chemicals in the most medicine, nearly all dyestuff all adopts aroamtic hydrocarbon raw material, and various auxiliary agents in the organic materials and advanced electronic material also all be unable to do without aroamtic hydrocarbon raw material.Aromatic hydrocarbons is mainly derived from refining of petroleum at present, and along with disposable petroleum resources tap/dip deep into and widely-used, output day by day reduces, and therefore develops new aromatic hydrocarbons production process, has important strategic meaning and realistic meaning.
Methyl alcohol is a kind of important chemical material, wide material sources.In recent years, the coal chemical industry engineering project starts comprehensively, and a collection of project that with the coal is raw material is produced methyl alcohol is built up one after another and gone into operation, and the production of methyl alcohol has entered a fast-developing period, and increase of production is huge.Along with progress of science and technology, be that chemical industry sintetics and new organic chemical industry's technology of raw material obtains paying attention to and development day by day with methyl alcohol, new chemical plant installations constantly is born, and Downstream Products of Methanol constantly produces, and impels the positive develop rapidly of methyl alcohol scientific and technological development.
At present, the Downstream Products of Methanol development field is wide, and speed is quite fast.As preparing gasoline by methanol (MTG), methyl alcohol system ethene (MTF) and methanol conversion are alkene (MTO) etc., and methyl alcohol prepares propylene and ethene is the importance achievement of the vertical deep development of methyl alcohol.The technology of the direct aromizing of methyl alcohol is demanded Application and Development urgently.
Utilize aromatization of methanol, be methyl alcohol under the effect of catalyzer, be the process of aromatic hydrocarbon through dehydration, polymerization and cyclisation, be to make rational use of resources to produce one of new effective way of aromatic hydrocarbons, be one of new problem that derives along with the development of Coal Chemical Industry in recent years, have certain strategic importance.Originally aromatization of methanol is a kind of byproduct in the preparing gasoline by methanol product; At present, specializing in the aromatization of methanol report only has 6 pieces, and wherein one piece is Chinese patent (application number 200610012703.1); Aromatics yield is only 30～40%.In the aromatization of methanol research process, as simple use HZSM-5 catalyzer, though produced aromatic hydrocarbons, but in aromatization process with side reactions such as cracking, hydrogenolysis, hydrogen transferences, produced other a large amount of hydrocarbon compounds simultaneously, restricted the raising of arenes selectivity, yield is not high.And with part or all of silicon or aluminium among the heteroatoms isomorphous substitution HZSM-5 such as copper, zinc, gallium, phosphorus, silver, in chemical constitution that has changed molecular sieve and pore structure size, the type of selecting to its surface acid property and molecular sieve carries out modulation, will obtain the molecular sieve catalyst of catalytic performance and selectivity excellence.The present invention is by the mixed and modified HZSM-5 molecular sieve catalyst of different activities ion, be intended to improve the selectivity of aromatization of methanol preparing aromatic hydrocarbon by converting, simultaneously find that in a large amount of research lanthanum has little effect for the modified HZSM-5 molecular sieve, different with in the past achievement in research.
Summary of the invention
The objective of the invention is to propose a kind of selectivity and yield that can improve aromatic hydrocarbon product, the aromatization of methanol that is suitable for suitability for industrialized production is again produced the preparation technology of aromatic hydrocarbons.
For achieving the above object, the present invention has adopted following technical scheme: be raw material with methyl alcohol, under the certain reaction condition, with the composite modified HZSM-5 molecular sieve catalyst of the active ion of different concns, catalysis methanol is produced aromatic hydrocarbons; HZSM-5 catalyzer (Si/Al is 25-100) wherein.Reaction can adopt fixed bed continuous processing or floating bed continuous processing to carry out, and as carrier gas, the flow through HZSM-5 molecular sieve catalyst of modification of carrying methanol steam is produced aromatic hydrocarbon product through catalysis with the nitrogen of certain air speed.In catalytic process, used the active ion modified HZSM-5 molecular sieve catalyst of different concns, use therein active ion one of has in copper, zinc, gallium, phosphorus, the silver or mixed assemblage, and the usage quantity of each active ion (load concentration) by weight is the 1-15% of molecular sieve.Catalytic reaction condition is: working pressure: 0.1-3.5Mpa; Service temperature: 380-500 ℃; Raw material liq air speed: 0.1-10.0h
-1N
2Air speed: 120-800h
-1
Technique effect of the present invention is: (1) has broken the kind and the concentration limit of the active ion that in the past is used for the modified HZSM-5 molecular sieve, and the matched combined mode of hybrid ionic modification, thereby expanded the method for modified catalyst greatly, made the yield of aromatic hydrocarbon product that very significantly increase arranged.(2) two components, three components or more polycomponent is mixed and modified have been given full play to the superiority of each component, can not only obviously improve the yield of aromatic hydrocarbons, and can improve the selectivity of aromatic hydrocarbon product by a relatively large margin.
Description of drawings
Fig. 1 is fluidizing reactor and revivifier synoptic diagram.
Embodiment
Below in conjunction with specific embodiment the present invention is described further, but is not limited to this.
Embodiment 1:
1. Preparation of catalysts
(1) taking by weighing commercially available Si/Al (atomic ratio) is 38 powdery HZSM-5 molecular sieve, 30 grams, 520 ℃ of following roastings 4 hours, to remove volatile constituent.
(2) get (1) molecular sieve 15 that obtains of step and restrain in mortar, add 5 gram pseudo-boehmite thorough mixing, grind evenly.
(3) nitric acid with 5Wt% drips in the good material of mill, mixes and pinches suitably, crosses 100 order sub-sieves, uses the Rotarytabletpress compressing tablet, puts into baking oven in 110 ℃ of oven dry.
(4) the sheet molecular sieve that makes is put into High Temperature Furnaces Heating Apparatus, adopt the ladder-elevating temperature method to be warming up to 120 ℃ earlier, constant temperature 0.5 hour, be warming up to 300 ℃ then, kept 1 hour, be warming up to 520 ℃ at last, kept 4 hours, to remove nitric acid and moisture etc., reduce to room temperature afterwards naturally and take out, being processed into tap density is that every gram is equivalent to the bulk about 1 milliliter.
(5) accurately take by weighing following reagent:
Cu(NO
3)
2.3H
2O 1.5～6.0g
Zn(NO
3)
2.6H
2O 4.0～14.0g
Ga(NO
3)
3.9H
2O 2.0～8.0g
(6) mentioned reagent is put into same beaker, complete with isopyknic water heating for dissolving, stir with glass stick.
(7) molecular sieve with step (4) adds in the solution of step (6) preparation, and 80 ℃ flooded 1 hour down, stir during this on time.To remain steeping fluid and incline to, and flood by the volume of the molecular sieve water-intake rate calculating of predicting, in the present embodiment, 15 mol sieve is used 14 milliliters of steeping fluids (illustrating: can adopt repeatedly dipping method) approximately.
(8) after the molecular sieve drying of dipping, with residue also diluted steeping fluid set by step (7) carry out double-steeping.
(9) treat that double-steeping liquid soaks fully and evaporate to dryness after, place 110 ℃ baking oven baking 2 hours, put into High Temperature Furnaces Heating Apparatus then, adopt gradient heating, be warming up to 150 ℃ earlier, constant temperature 0.5 hour continues to be warming up to 300 ℃, constant temperature 1 hour is warming up to 450 ℃ at last, is incubated 4 hours.The catalyzer that finally makes (Wt%) composed as follows:
Powdery HZSM-5 57.7～69.4
Zn 4.0～14.0
Cu 1.8～7.4
Ga 1.6～6.2
Intend thin water aluminium 19.2～23.1.
(10) in order to ensure the quality of catalyzer, guarantee better finishing of technology of aromatization, the traditional performance of detection molecules sieve catalyst was after roasting finished:
Hardness: 50～70N
Acid density: 0.2012～0.2531mmol/g
Strength of acid: 0.3986～0.7018mmol/g.
2. Aromatizatian catalytic reaction
Use fixed bed continuous processing (referring to Fig. 1), methyl alcohol with in certain flow injected system, after vaporization, is carried the HZSM-5 molecular sieve catalyst of the modification of descending to flow through at the nitrogen of certain air speed, obtain product based on aromatic hydrocarbons through catalysis; Wherein reaction conditions is:
Reaction pressure 2.3Mpa
400 ℃ of temperature of reaction
Raw material liq air speed 4.0h
-1
N
2Air speed 430h
-1
Product separates the gas phase lower carbon number hydrocarbons through refrigerated separation with liquid product.Isolate aromatic hydrocarbon product, yield is 60%-65Wt%.
Embodiment 2:
In the step (3), the material behind the 100 order sub-sieves can also be squeezed into the bar column type that diameter is 2-3mm with the spiral banded extruder excessively.
Utilize copper, zinc, gallium, phosphorus, silver-colored different kinds of ions mixed assemblage, press the foregoing description 1 and adopt fluidized-bed mode catalyzed reaction, the gained aromatics yield can reach 55-70Wt%.
Claims (5)
1, a kind ofly improves the technology that aromatization of methanol is produced arenes selectivity, it is characterized in that: be raw material with methyl alcohol, under the certain reaction condition, with the composite modified HZSM-5 molecular sieve catalyst of Ga, Zn, Cu, Cr, Ag active ion of different concns, catalysis methanol is produced aromatic hydrocarbon product.
2, raising aromatization of methanol according to claim 1 is produced the technology of arenes selectivity, it is characterized in that:
Described reaction conditions is:
Reaction pressure: 0.1-3.5MPa;
Temperature of reaction: 380-500 ℃;
Liquid methanol air speed ratio: 0.1-10.0h
-1
N
2Air speed ratio: 120-800h
-1
3, raising aromatization of methanol according to claim 1 and 2 is produced the technology of arenes selectivity, it is characterized in that: the preparation technology of described HZSM-5 molecular sieve catalyst may further comprise the steps:
(1),, removes volatile constituent 450-550 ℃ of following roasting 4 hours with powdery HZSM-5 molecular sieve;
(2) get an amount of (1) the HZSM-5 molecular sieve and a certain proportion of tackiness agent that obtain of step and put into the mortar thorough mixing, grind evenly;
(3) nitric acid with 1-5% drips in the good material of mill, mixes and pinches suitably, crosses 100 order sub-sieves, is squeezed into the bar column type that diameter is 2-3mm with the spiral banded extruder, and natural air drying changes over to then and carries out the gradient oven dry in the baking oven, and temperature controlling range is 90-120 ℃;
(4) the strip molecular sieve that makes is put into High Temperature Furnaces Heating Apparatus, adopt the ladder-elevating temperature method to be warming up to 100-120 ℃ earlier, constant temperature 0.5 hour, be warming up to 280-330 ℃ then, kept 1 hour, be warming up to 480-530 ℃ at last, kept 4 hours, to remove nitric acid and moisture, reduce to room temperature afterwards naturally and take out, being processed into tap density is that every gram is equivalent to the bulk about 1 milliliter;
(5) quantitatively take by weighing be used for the modified HZSM-5 molecular sieve active substance in same beaker, complete with isopyknic water heating for dissolving, stir with glass stick;
(6) molecular sieve of step (4) gained is added in the solution of step (5) preparation, 80 ℃ of dippings 1 hour down stir during this on time, and heat and will remain the steeping fluid evaporation, and flood by the equal-volume of the molecular sieve water-intake rate calculating of prediction;
(7) steeping fluid soak fully and evaporate to dryness after, place 100-120 ℃ baking oven to dry by the fire 2 hours, put into High Temperature Furnaces Heating Apparatus then, adopt gradient heating, be warming up to 120-160 ℃ earlier, constant temperature 0.5 hour, continue to be warming up to 280-320 ℃, constant temperature 1 hour is warming up to 430-490 ℃ at last, be incubated 4 hours, finally make the HZSM-5 molecular sieve catalyst of modification.
4, raising aromatization of methanol according to claim 3 is produced the technology of arenes selectivity, it is characterized in that: the described active substance that is used for the modified HZSM-5 molecular sieve is several mixed assemblages of gallium nitrate, zinc nitrate, cupric nitrate, phosphoric acid, Silver Nitrate, and load concentration is 1-15Wt%.
5, raising aromatization of methanol according to claim 3 is produced the technology of arenes selectivity, it is characterized in that: described tackiness agent can be pseudo-boehmite, γ-Al
2O
3Or any in the diatomite.
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| CN102910647A (en) * | 2011-08-02 | 2013-02-06 | 清华大学 | Catalyst for aromatic hydrocarbon preparation by means of conversion of methanol and/or dimethyl ether and preparation method and application of catalyst |
| CN103028436A (en) * | 2011-09-30 | 2013-04-10 | 中国石油化工股份有限公司 | Catalyst for preparing aromatic hydrocarbon by using methanol and preparation method of catalyst |
| CN103055928A (en) * | 2011-10-24 | 2013-04-24 | 中国石油化工股份有限公司 | Catalyst for preparing arene via direct methanol conversion and preparation method thereof |
| CN103357430A (en) * | 2012-03-30 | 2013-10-23 | 中国科学院大连化学物理研究所 | Cocrystallization molecular sieve catalyst for aromatization, as well as preparation method and application thereof |
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| CN103864561A (en) * | 2014-02-24 | 2014-06-18 | 中国海洋石油总公司 | Technical method for preparing aromatic hydrocarbon through methanol aromatization |
| CN103930205A (en) * | 2011-05-22 | 2014-07-16 | 弗纳技术股份有限公司 | Catalyst with an ion-modified binder |
| CN104250183A (en) * | 2013-06-26 | 2014-12-31 | 中石化洛阳工程有限公司 | Method for preparing aromatic hydrocarbons from methanol with low carbon olefin as byproduct, and apparatus thereof |
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