CN104588104A - Preparation method for catalyst used for preparation of dimethyl ether through dehydration of methanol - Google Patents
Preparation method for catalyst used for preparation of dimethyl ether through dehydration of methanol Download PDFInfo
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Abstract
The invention discloses a preparation method for a catalyst used for preparation of dimethyl ether through dehydration of methanol. The method comprises the following steps: adding heteropoly acid and a template agent into an aqueous solution containing organic acid so as to obtain a mixed solution, then adding a silicon source, uniformly mixing the silicon source with the mixed solution, carrying out stirring until a gel is formed and carrying out aging, drying and roasting so as to obtain a catalyst intermediate; and impregnating the catalyst intermediate with an alkane solvent at first and then with a heteropoly acid solution and carrying out drying and roasting so as to obtain the catalyst. According to the invention, the pore structure of the catalyst prepared by using the method can be improved; and surface active components of the catalyst are mainly composed of strongly acidic heteropoly acid and ammonium salts thereof, the dominated active component in the pore channel of the catalyst is an ammonium heteropoly acid salt with weak acidity, and thus, the catalyst has high conversion rate and selectivity, excessive cracking of products is avoided and high stability is obtained.
Description
Technical field
The present invention relates to a kind of preparation method of dimethyl ether by methanol dewater, particularly relate to the preparation method of a kind of carried heteropoly acid for preparing dimethyl ether by dewatering methanol (ammonium) salt catalyst.
Background technology
Dimethyl ether (Dimethy Ether, abbreviation DME) is a kind of colourless, non-toxic gas under normal temperature and pressure state, can compressedly be liquid.Dimethyl ether is important Organic Chemicals and chemical intermediate, can be used for the industries such as aerosol, cold-producing medium, alkylating agent, pharmacy, cosmetics, fuel.
Dimethyl ether, the earliest by obtained after the byproduct rectifying in high-pressure process methanol production, develops into methanol dehydration and synthesis gas directly synthesizes two kinds of techniques very soon.Liquid phase methanol dewatering preparing dimethy ether, reaction is carried out in the liquid phase, and major defect is that equipment corrosion is serious, operating condition severe, and environmental pollution is serious, and product post processing is more difficult to be eliminated gradually.And direct synthesis of dimethyl ether from synthesis gas still rests on the experimental study stage, the dominating process route producing dimethyl ether at present in the world remains vapor phase method methanol dehydration.
At present, the catalyst that methanol dehydration adopts is generally Al
2o
3or molecular sieve, wherein conventional molecular sieve has aluminum phosphate, HZSM-5, HY, SAPO etc., and they have respective shortcoming: although as high in aluminium oxide stability, reaction temperature is high, very high to the equipment requirement of reaction, causes high expensive; Molecular sieve catalysts acidity is comparatively strong, and initial temperature is low, but also there is the shortcoming of many, the easy carbon distributions of accessory substance, easy in inactivation.Because above catalyst also exists the shortcoming of self, make the preparation of dimethyl ether, investment is large, and cost is high, causes the production of dimethyl ether and use to be restricted.
CN101214451A discloses and heteropoly acid and transition metal oxide load is formed a kind of composite solid-acid catalyst on Nano-sized HZSM-5 zeolite.In the reaction of methanol gas phase dewatering preparing dimethy ether, when reaction temperature is 200
oduring C, the conversion ratio of methyl alcohol is higher than 85%, and dimethyl ether selectivity is higher than 99.5%.But because the specific surface of carrier is relatively little, can not the more heteropoly acid of load, make it lower in the catalytic activity of low temperature.
CN00102506.6 discloses a kind of catalyst of preparing dimethyl ether by dewatering methanol.This catalyst take aluminium oxide as carrier, and the active component of load is heteropoly acid, and anti-carbon deposit component is titanium dioxide and lanthanum sesquioxide, adopts infusion process preparation.Wang Shouguo etc. [molecular science journal 2001,2 (17): 99-104] report and are entitled as H
4siW
12o
40-La
2o
3/ γ-Al
2o
3the article of catalysis methanol dehydration dimethyl ether-preparing.Above-mentioned catalyst has higher catalytic activity and selective in the reaction, the optimum load amount of silico-tungstic acid is 10wt% ~ 16wt%, at ambient pressure, during for the treatment of pure methanol feedstock, it is selective higher, but its low temperature active is bad, and during for moisture methanol feedstock, its stability is bad, and selective and activity also declines thereupon.
Summary of the invention
In order to overcome weak point of the prior art, the invention provides a kind of preparation method of dimethyl ether by methanol dewater.This catalyst not only has high, selective good, the feature that carbon accumulation resisting ability is strong of low temperature active, and good stability.
The preparation method of described dimethyl ether by methanol dewater, comprising:
(1) heteropoly acid is joined containing in organic aqueous acid, obtain mixed solution;
(2) silicon source is joined in step (1) solution mix, then at 40 ~ 90 DEG C, be stirred to into gel, through aging;
(3) by the material of step (2) gained at 90 ~ 120 DEG C of drying 3.0 ~ 12.0h, then at 300 ~ 500 DEG C of roasting 2.0 ~ 6.0 h, obtain catalyst intermediate;
(4) catalyst intermediate that step (3) is obtained is joined in alkane solvent, then filter, be at room temperature dried to carrier surface without liquid phase;
(5) heteropoly acid solution is joined in the solid that step (4) obtains, at 40 ~ 90 DEG C, be stirred to solution evaporate to dryness;
(6) by the solid drying that step (5) obtains, then at 300 ~ 450 DEG C of roasting 2.0 ~ 6.0 h, catalyst is obtained.
When step (1) prepares mixed solution and/or in the heteropoly acid solution of step (5), add auxiliary agent presoma, preferably when step (1) prepares mixed solution and in the heteropoly acid solution of step (5), all add auxiliary agent presoma.Auxiliary agent presoma can be in lanthanum nitrate, cerous nitrate one or more.
Step (1) and the middle mol ratio introducing auxiliary agent presoma of step (5) are 4:1 ~ 1:4.
Step (1) and the middle mol ratio introducing heteropoly acid of step (5) are 4:1 ~ 1:4.
In step (1), heteropoly acid is one or more in phosphotungstic acid, silico-tungstic acid, phosphomolybdic acid; Organic acid is one or more in citric acid, tartaric acid, malic acid, and described organic acid and step (3) silicon source are with SiO
2the mol ratio of meter is 0.1 ~ 1.0.
Add template in step (1), template is one or more in DTAB, DTAC, softex kw, hexadecyltrimethylammonium chloride, Cetyltrimethylammonium bromide, OTAC, hexamethylenetetramine, and described template and step (2) silicon source are with SiO
2the mol ratio of meter is 0.01 ~ 1.0.
In step (2), described silicon source is one or more in ethyl orthosilicate, Ludox.
In step (2), described aging condition is as follows: at room temperature aging 8 h ~ 24 h.
In the catalyst intermediate of step (3) gained, active component exists with heteropoly acid ammonium salt form, and ammonium heteropoly acids is such as formula (1):
H
m(NH
4)
nYX
12O
40（1）
Wherein X represents W or Mo, and Y represents Si or P; When Y represents Si, m+n=4, n value is 0.1 ~ 2.0; When Y represents P, m+n=3, n value is 0.1 ~ 2.0.
In step (4), described alkane solvent is C
5~ C
10one or more in liquid n-alkane.The volume ratio of alkane solvent and catalyst intermediate is 1 ~ 3.Silica support adds in alkane solvent the time of carrying out flooding and is generally 5 min ~ 20 min.
In step (5), described heteropoly acid is one or more in phosphotungstic acid, silico-tungstic acid, phosphomolybdic acid.
In step (6), described drying condition is as follows: at 90 DEG C ~ 120 DEG C drying 3.0 h ~ 12.0 h.
Producing dimethyl ether by dehydrating methanol catalyst prepared by the inventive method, comprises active component, auxiliary agent and carrier, and active component is heteropoly acid and ammonium heteropoly acids, and auxiliary agent is lanthana and/or cerium oxide, and carrier is silica; With the weight of catalyst for benchmark, heteropoly acid and ammonium heteropoly acids are 5 % ~ 50 % in the total content of heteropoly acid, and be preferably 10 % ~ 40 %, auxiliary agent is 1 % ~ 20 % with the content of oxide basis, are preferably 1 % ~ 15 %, SiO
2content be 30 % ~ 94 %, be preferably 45 % ~ 89 %.
The character of producing dimethyl ether by dehydrating methanol catalyst prepared by the inventive method: specific area is 300 ~ 700 m
2/ g, pore volume is 0.40 ~ 0.70 mL/g, and average pore diameter is 4.0 ~ 6.0 nm.
Dimethyl ether by methanol dewater of the present invention is also applicable to moisture methanol feedstock dewatering preparing dimethy ether reaction.In the present invention, the reaction condition of methanol dehydration dimethyl ether-preparing is as follows: reaction pressure 0 ~ 4.0 MPa, mass space velocity 1.0 ~ 4.0 h
-1, reaction temperature 160 ~ 240 DEG C.
Dimethyl ether by methanol dewater prepared by the inventive method, not only can improve the pore structure of catalyst, and the active component on surface is based on the relatively strong heteropoly acid of acidity and ammonium salt thereof, active component in duct is based on the relatively weak ammonium heteropoly acids of acidity, ensure that the high conversion that catalyst has and selective, turn avoid the excessive fragmentation of product, and this catalyst also has higher stability.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in detail.In the present invention, wt% is mass fraction.
Embodiment 1
(1) catalyst preparing:
Take 8.9g lanthanum nitrate, 13.9g phosphotungstic acid, 120g softex kw and 168.8g citric acid are made into mixed solution, 249mL tetraethyl orthosilicate is joined in mixed solution, stir 2 h, then at 70 DEG C, gel is stirred to into, by gel at aged at room temperature 12 h, dry 8 h at 110 DEG C, then at 380 DEG C of roasting 3 h, gained solid joins in C6 alkane solvent, dipping 10min, then filter, at room temperature be dried to carrier surface without liquid phase, join in the aqueous solution containing 6.9g phosphotungstic acid and 4.4g lanthanum nitrate, solution evaporate to dryness is stirred at 70 DEG C, by the solid that obtains at 110 DEG C of drying 8.0 h, then at 450 DEG C of roasting 3.0 h, obtained catalyst, La
2o
3content is 5wt%, and phosphotungstic acid and amounts of ammonium salt are 20%.Wherein the mol ratio of softex kw and silica is 0.3, and the mol ratio of citric acid and silica is 0.8.Catalyst property lists in table 1.
(2) evaluation of catalyst:
The reaction of methyl alcohol (technical grade,>=98.5wt%) dewatering preparing dimethy ether is carried out in fixed-bed tube reactor, normal pressure, mass space velocity 2.5h
-1, reaction temperature 180 DEG C.Before reaction, catalyst is at N
2in 400 DEG C of activation 2 h under protection, be then down to after reaction temperature starts to react 4 hours, product is analyzed by gas-chromatography, calculates selective and conversion ratio, the results are shown in Table 2.
Embodiment 2
Take 13.3g lanthanum nitrate, 15.6g phosphotungstic acid, 182.2g softex kw and 96g citric acid are made into mixed solution, 227mL tetraethyl orthosilicate is joined in mixed solution, stir 2 h, then at 70 DEG C, gel is stirred to into, by gel at aged at room temperature 12 h, dry 8 h at 110 DEG C, then at 400 DEG C of roasting 3 h, gained solid joins in C6 alkane solvent, dipping 10min, then filter, at room temperature be dried to carrier surface without liquid phase, join in the aqueous solution containing 15.6g phosphotungstic acid and 13.3g lanthanum nitrate, solution evaporate to dryness is stirred at 70 DEG C, by the solid that obtains at 110 DEG C of drying 8.0 h, then at 430 DEG C of roasting 3.0 h, obtained catalyst, La
2o
3content is 10wt%, and phosphotungstic acid and amounts of ammonium salt are 30%.Wherein the mol ratio of softex kw and silica is 0.5, and the mol ratio of citric acid and silica is 0.5.Catalyst property lists in table 1.
The evaluation of catalyst is with embodiment 1, and conversion ratio and the selective of crackate the results are shown in Table 2.
Embodiment 3
Take 13.3g lanthanum nitrate, 12.1g phosphotungstic acid, 243g softex kw and 48g citric acid are made into mixed solution, 189mL tetraethyl orthosilicate is joined in mixed solution, stir 2 h, then at 70 DEG C, gel is stirred to into, by gel at aged at room temperature 12 h, dry 8 h at 110 DEG C, then at 420 DEG C of thermal bake-out 3 h, gained solid joins in C6 alkane solvent, dipping 10min, then filter, at room temperature be dried to carrier surface without liquid phase, join in the aqueous solution containing 26.6g phosphotungstic acid and 24.2g lanthanum nitrate, solution evaporate to dryness is stirred at 70 DEG C, by the solid that obtains at 110 DEG C of drying 8.0 h, then at 400 DEG C of roasting 3.0 h, obtained catalyst, La
2o
3content is 15wt%, and phosphotungstic acid and amounts of ammonium salt are 35%.Wherein the mol ratio of softex kw and silica is 0.8, and the mol ratio of citric acid and silica is 0.3.Catalyst property lists in table 1.
The evaluation of catalyst is with embodiment 1, and conversion ratio and the selective of crackate the results are shown in Table 2.
Embodiment 4
In example 2, softex kw is changed into 196.2g octadecyl trimethyl bromine
Change ammonium, lanthanum nitrate changes 25.2g cerous nitrate into, and all the other are with embodiment 2, obtained catalyst, wherein CeO
2content is 10wt%, Macrogol 4000 and SiO
2mol ratio be 0.1.Catalyst property lists in table 1.
The evaluation of catalyst is with embodiment 1, and conversion ratio and the selective of crackate the results are shown in Table 2.
Embodiment 5
In example 2, change phosphotungstic acid into silico-tungstic acid, softex kw changes 154.2g into
DTAB, all the other are with embodiment 2, obtained catalyst.Catalyst property lists in table 1.
The evaluation of catalyst is with embodiment 1, and conversion ratio and the selective of crackate the results are shown in Table 2.
Embodiment 6
Obtain catalyst according to embodiment 2, the appreciation condition according to embodiment 2 is tested the estimation of stability that catalyst has carried out 100 h, and conversion ratio and the selective of crackate the results are shown in Table 3.
Embodiment 7
Compared with embodiment 6, difference is: in evaluating catalyst, and changed into by methanol feedstock and change the methyl alcohol that purity is 95wt% into, wherein moisture 5wt%, all the other are with embodiment 6.
The evaluation of catalyst is with embodiment 1, and conversion ratio and the selective of crackate the results are shown in Table 3.
Comparative example 1
Take 182.2g softex kw and 96g citric acid is made into mixed solution, 227mL tetraethyl orthosilicate is joined in mixed solution, stir 2 h, then at 70 DEG C, gel is stirred to into, by gel at aged at room temperature 12 h, dry 8 h at 110 DEG C, then at 430 DEG C of roasting 3 h, obtain catalyst carrier.Carrier is directly joined in the mixed aqueous solution containing 26.6g lanthanum nitrate and 31.2g phosphotungstic acid, at 70 DEG C, be stirred to solution evaporate to dryness; By the solid that obtains at 110 DEG C of drying 8.0 h, then at 350 DEG C of roasting 3.0 h, obtained H
3pW
12o
40-La
2o
3/ SiO
2catalyst, wherein La
2o
3content is 10wt%, H
3pW
12o
40content is 30wt%.Catalyst property lists in table 1.
The evaluation of catalyst is with embodiment 1, and conversion ratio and the selective of crackate the results are shown in Table 2.
Comparative example 2
Obtain catalyst according to comparative example 1, the appreciation condition according to comparative example 1 is tested the estimation of stability that catalyst has carried out 100 h, and conversion ratio and the selective of crackate the results are shown in Table 3.
Comparative example 3
Obtain catalyst according to comparative example 1, the appreciation condition according to embodiment 7 is tested the estimation of stability that catalyst has carried out 100 h, and conversion ratio and the selective of crackate the results are shown in Table 3.
The character of each routine catalyst of table 1
The conversion ratio of each routine catalyst of table 2 and selective
Table 3 stability test evaluation result
Claims (15)
1. a preparation method for dimethyl ether by methanol dewater, comprising:
(1) heteropoly acid and template are joined containing in organic aqueous acid, obtain mixed solution; Template is one or more in DTAB, DTAC, softex kw, hexadecyltrimethylammonium chloride, Cetyltrimethylammonium bromide, OTAC, hexamethylenetetramine, and described template and step (2) silicon source are with SiO
2the mol ratio of meter is 0.01 ~ 1.0;
(2) silicon source is joined in step (1) solution mix, then at 40 ~ 90 DEG C, be stirred to into gel, through aging;
(3) by the material of step (2) gained at 90 ~ 120 DEG C of drying 3.0 ~ 12.0 h, then at 300 ~ 500 DEG C of roasting 2.0 ~ 6.0 h, obtain catalyst intermediate;
(4) catalyst intermediate that step (3) is obtained is joined in alkane solvent, then filter, be at room temperature dried to carrier surface without liquid phase;
(5) heteropoly acid solution is joined in the solid that step (4) obtains, at 40 ~ 90 DEG C, be stirred to solution evaporate to dryness;
(6) by the solid drying that step (5) obtains, then at 300 ~ 450 DEG C of roasting 2.0 ~ 6.0 h, catalyst is obtained.
2. in accordance with the method for claim 1, it is characterized in that adding auxiliary agent presoma when step (1) prepares mixed solution and/or in the heteropoly acid solution of step (5), auxiliary agent presoma is one or more in lanthanum nitrate, cerous nitrate.
3. in accordance with the method for claim 2, it is characterized in that the mol ratio introducing auxiliary agent presoma in step (1) and step (5) is 4:1 ~ 1:4.
4. in accordance with the method for claim 1, it is characterized in that the mol ratio introducing heteropoly acid in step (1) and step (5) is 4:1 ~ 1:4.
5. in accordance with the method for claim 1, it is characterized in that in step (1), heteropoly acid is one or more in phosphotungstic acid, silico-tungstic acid, phosphomolybdic acid; Organic acid is one or more in citric acid, tartaric acid, malic acid, and described organic acid and step (2) silicon source are with SiO
2the mol ratio of meter is 0.1 ~ 1.0.
6. in accordance with the method for claim 1, it is characterized in that in step (2), described silicon source is one or more in ethyl orthosilicate, Ludox.
7. in accordance with the method for claim 1, it is characterized in that in step (2), described aging condition is as follows: at room temperature aging 8 h ~ 24 h.
8. in accordance with the method for claim 1, it is characterized in that in the catalyst intermediate of step (3) gained, active component exists with heteropoly acid ammonium salt form, and ammonium heteropoly acids is such as formula (1):
H
m(NH
4)
nYX
12O
40（1）
Wherein X represents W or Mo, and Y represents Si or P; When Y represents Si, m+n=4, n value is 0.1 ~ 2.0; When Y represents P, m+n=3, n value is 0.1 ~ 2.0.
9. in accordance with the method for claim 1, it is characterized in that described producing dimethyl ether by dehydrating methanol catalyst, comprise active component, auxiliary agent and carrier, active component is heteropoly acid and ammonium heteropoly acids, and auxiliary agent is lanthana and/or cerium oxide, and carrier is silica; With the weight of catalyst for benchmark, heteropoly acid and ammonium heteropoly acids are 5 % ~ 50 % in the total content of heteropoly acid, and auxiliary agent is 1 % ~ 20 %, SiO with the content of oxide basis
2content be 30 % ~ 94 %.
10. in accordance with the method for claim 1, it is characterized in that in described producing dimethyl ether by dehydrating methanol catalyst, with the weight of catalyst for benchmark, heteropoly acid and ammonium heteropoly acids are 10 % ~ 40 % in the total content of heteropoly acid, auxiliary agent is 1 % ~ 15 %, SiO with the content of oxide basis
2content be 45 % ~ 89 %.
11. in accordance with the method for claim 1, it is characterized in that, in step (4), described alkane solvent is C
5~ C
10one or more in liquid n-alkane, the volume ratio of alkane solvent and catalyst intermediate is 1 ~ 3, and it is 5 min ~ 20 min that silica support adds in alkane solvent the time of carrying out flooding.
12. in accordance with the method for claim 1, it is characterized in that in step (5), and described heteropoly acid is one or more in phosphotungstic acid, silico-tungstic acid, phosphomolybdic acid.
13. in accordance with the method for claim 1, it is characterized in that in step (6), described drying condition is as follows: at 90 DEG C ~ 120 DEG C drying 3.0 h ~ 12.0 h.
14. 1 kinds of producing dimethyl ether by dehydrating methanol catalyst, is characterized in that adopting the arbitrary described method of claim 1 ~ 13 to prepare.
15. according to catalyst according to claim 14, it is characterized in that the character of described producing dimethyl ether by dehydrating methanol catalyst: specific area is 300 ~ 700 m
2/ g, pore volume is 0.40 ~ 0.70 mL/g, and average pore diameter is 4.0 ~ 6.0 nm.
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| CN106944146B (en) * | 2016-01-07 | 2019-06-11 | 中国石油化工股份有限公司 | A kind of preparation method of heteropoly acid ammonium catalyst |
| CN109926074A (en) * | 2017-12-15 | 2019-06-25 | 中国石油化工股份有限公司 | Hydrocracking catalyst and preparation method thereof |
| CN109926094A (en) * | 2017-12-15 | 2019-06-25 | 中国石油化工股份有限公司 | A kind of hydrocracking catalyst and its preparation method |
| CN109926094B (en) * | 2017-12-15 | 2021-08-06 | 中国石油化工股份有限公司 | Hydrocracking catalyst and preparation method thereof |
| CN109926074B (en) * | 2017-12-15 | 2021-08-06 | 中国石油化工股份有限公司 | Hydrocracking catalyst and preparation method thereof |
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