CN100336589C - Catalyst for preparing dimethyl ether from synthetic gas by one step - Google Patents
Catalyst for preparing dimethyl ether from synthetic gas by one step Download PDFInfo
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- CN100336589C CN100336589C CNB2004100177135A CN200410017713A CN100336589C CN 100336589 C CN100336589 C CN 100336589C CN B2004100177135 A CNB2004100177135 A CN B2004100177135A CN 200410017713 A CN200410017713 A CN 200410017713A CN 100336589 C CN100336589 C CN 100336589C
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- dimethyl ether
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- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 title claims abstract description 136
- 239000003054 catalyst Substances 0.000 title claims abstract description 87
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 207
- 239000002808 molecular sieve Substances 0.000 claims abstract description 39
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910052796 boron Inorganic materials 0.000 claims abstract description 28
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 20
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 31
- 230000018044 dehydration Effects 0.000 claims description 29
- 238000006297 dehydration reaction Methods 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 27
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 26
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 26
- 230000015572 biosynthetic process Effects 0.000 claims description 26
- 238000003786 synthesis reaction Methods 0.000 claims description 26
- 238000002360 preparation method Methods 0.000 claims description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- 230000004048 modification Effects 0.000 claims description 16
- 238000012986 modification Methods 0.000 claims description 16
- 229910052782 aluminium Inorganic materials 0.000 claims description 14
- 239000011787 zinc oxide Substances 0.000 claims description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 10
- 229910052802 copper Inorganic materials 0.000 claims description 10
- 239000010949 copper Substances 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 9
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- 229910021536 Zeolite Inorganic materials 0.000 claims description 7
- 239000010457 zeolite Substances 0.000 claims description 7
- 239000004411 aluminium Substances 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052810 boron oxide Inorganic materials 0.000 claims description 5
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 5
- 238000001802 infusion Methods 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- 229960004643 cupric oxide Drugs 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000005342 ion exchange Methods 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 63
- 230000002194 synthesizing effect Effects 0.000 abstract description 4
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 40
- 208000005156 Dehydration Diseases 0.000 description 27
- 230000001588 bifunctional effect Effects 0.000 description 24
- 229910002091 carbon monoxide Inorganic materials 0.000 description 20
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 18
- 229930195733 hydrocarbon Natural products 0.000 description 15
- 150000002430 hydrocarbons Chemical class 0.000 description 15
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 14
- 239000004327 boric acid Substances 0.000 description 14
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 10
- 239000002245 particle Substances 0.000 description 10
- 238000010298 pulverizing process Methods 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 9
- 239000000320 mechanical mixture Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 230000002378 acidificating effect Effects 0.000 description 8
- 239000012153 distilled water Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 230000009257 reactivity Effects 0.000 description 7
- 238000011160 research Methods 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 description 5
- 239000001569 carbon dioxide Substances 0.000 description 5
- 238000007598 dipping method Methods 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 238000010335 hydrothermal treatment Methods 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000000295 complement effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000002283 diesel fuel Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- 229910017773 Cu-Zn-Al Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012013 faujasite Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a catalyst for once preparing dimethyl ether from synthetic gas, and mainly solves the problems that the existing catalysts have high reaction temperature, low CO conversion rate and/or low selectivity of dimethyl ether. The present invention effectively and directly once converts synthetic gas into dimethyl ether and solves the technical problems through a technical scheme in which dual-purpose catalysts are adopted and HZSM-5 molecular sieves modified by boron are taken as a component for dewatering methanol and compounded with a component for synthesizing copper-zinc based methanol. Therefore, the present invention can be used in the industrial production of once preparing dimethyl ether.
Description
Technical field
The present invention relates to a kind of catalyst by synthesis gas one step preparation dimethyl ether.
Background technology
Dimethyl ether is mainly used in the propellant of aerosol because of its distinctive physicochemical property.In addition, dimethyl ether also can be used as the industrial chemicals of synthetic sulfuric acid dimethyl ether etc., substitute diesel oil and be used for domestic fuel etc. as clean automobile fuel and replacement liquid gasification, especially in recent years the one-step method from syngas technology progressively develops, the construction of large-scale dimethyl ether process units is brought into schedule, and the development prospect of its alternative diesel oil or liquefied gas aspect is generally had an optimistic view of.
Dimethyl ether is by making after the byproduct rectifying in the high pressure methanol production the earliest.Along with the low pressure methanol synthesis broad application, side reaction significantly reduces, and the dimethylether industrial production technology develops into methanol dehydration or synthesis gas direct synthesis process very soon, promptly so-called two-step method and one-step method.Two-step method is earlier synthesis gas to be converted into methyl alcohol, then methanol dehydration is converted into dimethyl ether.The methanol dehydration method comprises two kinds of liquid phase method and vapor phase methods.The former is reflected in the liquid phase and carries out, and methyl alcohol makes through concentrated sulfuric acid dehydration.This technology has reaction condition gentleness (130～160 ℃), methyl alcohol conversion per pass height (about 90%), but can be intermittently also quantity-produced advantage.But, progressively be eliminated because of there are problems such as equipment corrosion, environmental pollution, operating condition be abominable in this method.Because the dimethyl ether demand growth is very fast, various countries develop reduced investment again in succession, operating condition is good, free of contamination methanol gas phase dehydration method new technology.Research and develop out the methanol vapor phase method dewatering preparing dimethy ether method of utilizing crystalline aluminosilicate to make catalyst as nineteen sixty-five Mobil company.Early 1980s Mobil company improves catalysis again, and dimethyl ether selectivity and methanol conversion are all improved a lot.Mitsui east pressed chemical company also to develop new catalyst in 1991.Domestic southwestern chemical research institute and Shanghai petrochemical industry research institute etc. have also all developed the catalyst of methanol gas phase dehydration, and are applied on the commercial plant of different scales.
Directly producing dimethyl ether by synthesis gas is that one-step technology is a kind of new technology of developing in recent years, exactly synthetic being reflected in the same reactor with two of methanol dehydrations of methyl alcohol there is not pilot process, because there is the synthetic and methanol dehydration two classes reaction of methyl alcohol simultaneously in reaction system, therefore broken the thermodynamics equilibrium limit that exists in the simple methyl alcohol building-up process, produce bigger forward reaction motive force, thereby can reduce the conversion per pass of operating pressure and raising CO effectively.In general, one-step method is better than two step method, so the domestic and international at present research about dimethyl ether mainly concentrates on the research to one-step method.
Reaction by directed preparing dimethyl ether by synthetic gas can be divided into following a few step:
2CO+4H
2＝2CH
3OH ΔH＝-180.58kJ (1)
2CH
3OH＝CH
3OCH
3+H
2O ΔH＝-23.41kJ (2)
H
2O+CO＝H
2+CO
2 ΔH＝-40.96kJ (3)
(1)+(2)：2CO+4H
2→CH
3OCH
3+H
2O ΔH＝-180.58kJ (4)
(1)+(2)+(3)：3CO+3H
2→CH
3OCH
3+CO
2ΔH＝-180.58kJ (5)
By above-mentioned reaction as can be seen:
The methyl alcohol that generates in formula (1) is consumed generation dimethyl ether and water in formula (2), the water generation transformationreation that is generated generates CO
2And H
2, and the H that generates
2It is again the raw material of synthesizing methanol.The product that each step reaction is generated is the reactant of another step reaction, and this can not be subjected to the thermodynamic limitation of synthesizing methanol just for entire reaction has produced very big motive force, thereby obtains higher CO conversion rate.
The bifunctional catalyst of the catalyst that one-step method adopted for being composited by methanol synthesis catalyst and methanol dehydration catalyst.Methanol synthesis catalyst is mainly the copper base oxide catalyst, as composite oxides such as Cu-Zn-Al or Cu-Zn-Cr.Methanol dehydration catalyst is mainly solid acid catalysts such as aluminium oxide, molecular sieve or aluminum phosphate, wherein, and γ-Al
2O
3With the HZSM-5 molecular sieve be with the most use two kinds.
The U.S. Pat 4375424 (1983) that is entitled as " catalyst of preparation dimethyl ether " has disclosed the employing infusion process the synthetic component copper-zinc of methyl alcohol has been loaded on acidic components γ-Al
2O
3On the bifunctional catalyst that forms.At H
2/ CO mol ratio is 1: 1, about 300 ℃ of reaction temperature, reaction pressure 12MPa and unstripped gas air speed 3000 hours
-1Reaction condition under, the conversion ratio of carbon monoxide is 60～70%.See that thus reaction pressure that above-mentioned catalyst is required and reaction temperature are all higher, and reactivity lower (the highest be no more than 70%).
It is that synthetic component of methyl alcohol and aluminium oxide are the bifunctional catalyst that the methanol dehydration component is composited that the Chinese patent CN 1233527A (1999) that is entitled as the Catalysts and its preparation method of dimethyl ether synthesis " directly " has disclosed with oxides such as copper, manganese.At H
2/ CO mol ratio is 3/2,250～270 ℃ of reaction temperatures, reaction pressure 4MPa and unstripped gas air speed 1500 hours
-1Reaction condition under, the conversion ratio of carbon monoxide is 82.59%.See that thus the reactivity of above-mentioned catalyst is still lower.
It is that synthetic component of methyl alcohol and aluminium oxide are the bifunctional catalyst that the methanol dehydration component is composited that the Chinese patent CN1356163A (2002) that is entitled as the bifunctional catalyst and the preparation technology thereof of synthesis gas preparing dimethy ether " directly by " has disclosed with composite oxides such as copper, zinc.At H
2/ CO mol ratio is 3.85, reaction temperature is 300 ℃, reaction pressure 4MPa and unstripped gas air speed 1490 hours
-1Reaction condition under, the conversion ratio of carbon monoxide is 81.75%, the dimethyl ether selectivity is 93.56%.This shows that the reaction temperature of above-mentioned catalyst is higher, the conversion ratio of carbon monoxide is lower.
Because active A l
2O
3Optimum activity temperature as methanol dehydration catalyst higher (about 300 ℃), the optimum activity temperature (about 250 ℃) of synthesizing the copper-based catalysts of component with methyl alcohol is not complementary.So, adopt active A l
2O
3Prepare bifunctional catalyst as methanol dehydration and have following shortcoming: (1) is as if carrying out under the optimum activity temperature that is reflected at copper-based catalysts, because active A l
2O
3Dewatering under this temperature is relatively poor, and not only the selectivity of dimethyl ether is lower in the product, and because the advantage of one-step method can't be fully played, the conversion ratio of carbon monoxide is also lower; (2) if be reflected at active A l
2O
3The optimum activity temperature under carry out, because the reaction by preparation of dimethyl ether from synthesis gas is a course of reaction that low temperature is favourable, so, under higher reaction temperature, be difficult to obtain higher carbon monoxide conversion ratio, and higher reaction temperature helps the generation of hydro carbons accessory substance, thereby also can cause the selectivity of dimethyl ether in the product to reduce.
Because γ-Al
2O
3The optimum activity temperature and the optimum activity temperature of the copper-based catalysts of the synthetic component of methyl alcohol be not complementary, cause the performance of bifunctional catalyst to reduce.For this reason, people have carried out with the research of various molecular sieve catalysts as the methanol dehydration component.
The Chinese patent CN 1087033A (1994) that is entitled as " being converted into the dimethyl ether metallic zeolite catalyst for reaction by synthesis gas " has disclosed with H type faujasite or modenite and the H type Y after hydrothermal treatment consists or the modenite bifunctional catalyst as the methanol dehydration component.This catalyst is at H
2/ CO mol ratio is 2,260 ℃ of reaction temperatures, reaction pressure 3.5MPa and unstripped gas air speed 1000 hours
-1Reaction condition under, the conversion ratio of carbon monoxide reaches as high as 90%, the dimethyl ether selectivity is more than 90%.
Ge Qingjie, (gas chemical industry, 1996,21 (6): result 16) also shows Huang Youmei, replaces γ-Al with HSY or HZSM-5
2O
3Make dehydration component, can make the active temperature of bifunctional catalyst be reduced to 250～260 ℃ from 280～290 ℃; And the selectivity of dimethyl ether and space-time yield all increase.
Chen Jiangang, Niu Yuqin (gas chemical industry, 1997,22 (6): 6) studied of the influence of the silica alumina ratio of HZSM-5 molecular sieve to the bifunctional catalyst reactivity worth, the result shows that the silica alumina ratio of HZSM-5 molecular sieve optionally influences very obvious to dimethyl ether, along with the increase of HZSM-5 molecular sieve silica alumina ratio, the selectivity of dimethyl ether raises.
Tan give birth to wait (Journal of Molecular Catalysis, 1999,13 (4): 246) the HZSM-5 molecular sieve of then having studied with hydrothermal treatment consists is the influence of dehydration component to bifunctional catalyst, the result shows the raising along with the hydrothermal treatment consists temperature, the selectivity of dimethyl ether improves thereupon.
Above-mentioned result of study shows that all the weak acid center on HZSM-5 molecular sieve surface helps the generation of dimethyl ether, the strong acid center generation hydro carbons that then methyl alcohol and dimethyl ether further dewatered, thus reduced the selectivity of dimethyl ether in the product.So if the silica alumina ratio of HZSM-5 molecular sieve is too low, because of there being more strong acid center, the selectivity of dimethyl ether reduces in the product that can induce reaction; If silica alumina ratio is too high, though the selectivity of dimethyl ether can be very high, because the acid amount is less, its dehydration activity must reduce.Though hydrothermal treatment consists can make the strong acid center on molecular sieve surface significantly reduce, also reduced the weak acid center simultaneously, thereby reduced reactivity.
Summary of the invention
Technical problem to be solved by this invention is reaction temperature height, carbon monoxide conversion ratio and/or the low problem of dimethyl ether selectivity that has catalyst in the prior art, and a kind of new catalyst by synthesis gas one step preparation dimethyl ether is provided.Use that this catalyst has that reaction temperature is low, carbon monoxide conversion ratio height and the good advantage of dimethyl ether selectivity.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of catalyst by synthesis gas one step preparation dimethyl ether comprises following component by weight percentage:
A) in the copper of cupric oxide 10～70%;
B) in the zinc of zinc oxide 5～50%;
C) silica alumina ratio SiO
2/ Al
2O
3It is 10～140 H-ZSM type zeolite 10～60%;
D) in the boron of boron oxide 0.1～10%;
E) in the aluminium of aluminium oxide 0.1～10%;
Wherein said boron adds on the H-ZSM type molecular sieve by ion-exchange, infusion process or mechanical mixing, drying and 250～750 ℃ of roastings then, thus make boron modification H-ZSM type molecular sieve as the methanol dehydration component in the catalyst.
In the technique scheme, the amount of copper is 25～50% in the cupric oxide preferable range by weight percentage, the amount of zinc is 10～30% in the zinc oxide preferable range, the amount preferable range of H-ZSM type zeolite is 20～50%, the amount of boron is 0.5～5% in the boron oxide preferable range, and the amount of aluminium is 3～7% in the aluminium oxide preferable range.H-ZSM type zeolite preferred version is for being selected from H-ZSM-5.The preferred version of aluminium is for to exist with the gama-alumina form.
Preparation of Catalyst of the present invention adopts common mechanical mixing, infusion process or coprecipitation preparation.Wherein the boron modifier in the catalyst is to add on the H-ZSM type molecular sieve by methods such as ion-exchange, infusion process or mechanical mixings, and drying and high-temperature roasting make then.Sintering temperature is 250～750 ℃, more preferably 350～650 ℃.The adding form of additive can be their oxide or the compound of boracic, as boron oxide and boric acid etc.
The reason that its reactivity worth of bifunctional catalyst for preparing as the methanol dehydration component with boron modification H-ZSM type molecular sieve of the present invention is significantly increased mainly is because the change of its acidity.Acid characterization (NH
3-TPD) result shows, the H-ZSM type molecular sieve strong acid center number after the modification obviously reduces, and the weak acid center does not have obvious variation.Because the methanol dehydration step in the preparing dimethylether from synthetic gas by reaction is mainly carried out on the weak acid position, side reaction significantly reduces as dehydration component with the H-ZSM type molecular sieve after the modification like this, thereby improved the dimethyl ether selectivity and the stability of catalyst greatly, obtained better technical effect.
Bifunctional catalyst of the present invention can be used for fixed bed reactors and fluidized-bed reactor, and also can be used for gas-liquid-solid three-phase bed reactor is paste state bed reactor.
The catalyst of the present invention preparation before reaction preferred version for reducing processing earlier.The mixture that consists of hydrogen and inert gas of reducing gases, inert gas are one or more the mixture in nitrogen, helium and the argon gas etc.The volume content of hydrogen is 0.5～20% in the reducing gases, is preferably 1～10%; Reduction temperature is 180～300 ℃, is preferably 220～280 ℃; The air speed of reducing gases is 500～5000 hours
-1, be preferably 1000～3000 hours
-1
Catalyst of the present invention is used for direct preparation of dimethyl ether by using synthesis gas, and its reaction condition that is suitable for is: the mol ratio of raw material of synthetic gas hydrogen and carbon monoxide is 0.8: 1～5: 1, is preferably 1: 1～3: 1; And preferably contain a certain amount of carbon dioxide in the gaseous mixture, its volumn concentration is 0.5～10%, is preferably 1～5%.The volume space velocity of reaction gas is 100～10000 hours
-1, be preferably 500～3000 hours
-1Reaction temperature is 200～400 ℃, is preferably 220～300 ℃.Reaction pressure is 2.0～8.0MPa, is preferably 3.5～6.0MPa.
An example of the present invention that uses fixed bed reactors is hereinafter described.
It is 6 millimeters that a certain amount of catalyst granules (20～40 order) is loaded in internal diameter, and length is in 300 millimeters the stainless steel reactor.Adopt electrical heating, temperature is controlled automatically.Reactor bottom filling 20～40 purpose inert materials are as supporter, a certain amount of catalyst of filling in the reactor, and filling 20～40 purpose inert materials in catalyst top are made for the usefulness of raw material preheating.Co hydrogenation and Dehydration of methanol take place from top to bottom by beds in material synthesis gas, generate purpose product dimethyl ether and accessory substances such as methyl alcohol and a spot of alkane.Catalyst filling back reducing gases (5%H
2/ 95%N
2) after (240 ℃) reduction that heats up, switch unstripped gas and react.The composition of unstripped gas (volume fraction) is CO:31.1%, CO
2: 5.7%, all the other are H
2Reaction pressure 4.0MPa; Reaction temperature is 230 ℃～290 ℃; The volume space velocity of unstripped gas is 1500 hours
-1Adopt HP 4890D type gas chromatograph to carry out on-line analysis, use thermal conductivity detector (TCD), carbon molecular sieve chromatogram column analysis carbon monoxide and carbon dioxide; Use hydrogen flame ionization detector, Porapak-N chromatogram column analysis methyl alcohol, dimethyl ether and hydro carbons accessory substance.
According to each components contents in the reaction end gas, adopt following formula to calculate the conversion ratio of carbon monoxide and the selectivity of the hydro carbons in the product, methyl alcohol and dimethyl ether in the molal quantity of carbon atom:
Carbon monoxide conversion ratio (%)=(amount of the amount+dimethyl ether of the amount+methyl alcohol of the amount+hydro carbons of carbon dioxide * 2)/(amount of the amount+dimethyl ether of the amount+methyl alcohol of the amount+hydro carbons of the amount+carbon dioxide of carbon monoxide * 2) * 100%
The amount of the selectivity=dimethyl ether of dimethyl ether * 2/ (amount of the amount+dimethyl ether of hydro carbons * 2) * 100%
The amount of the selectivity=methyl alcohol of methyl alcohol/(amount of the amount+dimethyl ether of the amount+methyl alcohol of hydro carbons * 2) * 100%
The amount of the selectivity=hydro carbons of hydro carbons/(amount of the amount+dimethyl ether of the amount+methyl alcohol of hydro carbons * 2) * 100%
The invention will be further described below by embodiment, but do not limit its scope.
The specific embodiment
[embodiment 1]
3.6 gram boric acid are made into 100 milliliters boric acid aqueous solution with dissolved in distilled water, then toward wherein pouring 100 gram H-ZSM-5 molecular sieve (silica alumina ratio SiO into
2/ Al
2O
3=76), dipping 1～2 hour after 110 ℃ of oven dry spend the night after again at 500 ℃ of roastings 3 hours molecular sieve B-H-ZSM-5 to the boron modification.With above-mentioned resulting B-H-ZSM-5 is acidic components, carries out mechanical mixture, compressing tablet, pulverizing and sieve with the synthetic component of methyl alcohol and gets 20～40 purpose particles and obtain bifunctional catalyst A, and wherein the weight percentage of each component is CuO 45.3%, and ZnO 20%, Al
2O
33%, H-ZSM-5 31%, B
2O
30.7%.
[embodiment 2]
10 gram boric acid are made into 400 milliliters boric acid aqueous solution with dissolved in distilled water, then toward wherein pouring 40 gram H-ZSM-5 molecular sieve (SiO into
2/ Al
2O
3Mol ratio=76), flood elimination raffinate after 1～2 hour, after 110 ℃ of oven dry are spent the night, obtained the molecular sieve B-H-ZSM-5 of boron modification again 550 ℃ of roastings in 3 hours.With above-mentioned resulting B-H-ZSM-5 is acidic components, carries out mechanical mixture, compressing tablet, pulverizing and sieve with the synthetic component of methyl alcohol and gets 20～40 purpose particles and obtain bifunctional catalyst B, and wherein the weight percentage of each component is CuO 40%, and ZnO 25%, Al
2O
34%, H-ZSM-5 30%, B
2O
31%.
[embodiment 3]
With 1.0 gram boric acid and 10 gram H-ZSM-5 molecular sieve (SiO
2/ Al
2O
3Mol ratio=76) in grinding alms bowl, fully be milled to and mix, obtained the molecular sieve B-H-ZSM-5 of boron modification then 450 ℃ of roastings in 3 hours.With above-mentioned resulting B-H-ZSM-5 is acidic components, carries out mechanical mixture, compressing tablet, pulverizing and sieve with the synthetic component of methyl alcohol and gets 20～40 purpose particles and obtain bifunctional catalyst C, and wherein the weight percentage of each component is CuO 34%, and ZnO 14%, Al
2O
32%, H-ZSM-5 46%, B
2O
34%.
[embodiment 4]
The H-ZSM-5 molecular sieve of resulting boron modification in the foregoing description 1 is dissolved in a certain amount of distilled water, under strong agitation, contain a certain amount of copper nitrate then toward wherein splashing into simultaneously, the mixed solution of zinc nitrate and aluminum nitrate and sodium carbonate liquor, after dropwising being deposited in of gained continued in the mother liquor to stir 1 hour, resulting precipitation is used the distilled water cyclic washing after filtering, through 110 ℃ dry after 350 ℃ of following roastings 6 hours, after compressing tablet, pulverizing and sieve are got 20～40 purpose particles and are obtained bifunctional catalyst D, wherein the weight percentage of each component is CuO 36%, ZnO 20%, Al
2O
34%, H-ZSM-5 39%, B
2O
31%.
[comparative example 1]
Replacing B-HZSM-5 molecular sieve among the embodiment 1 and methanol synthesis catalyst to carry out mechanical mixture, compressing tablet, pulverizing and sieve with the H-ZSM-5 molecular sieve (Si/Al=38) of non-modified gets 20～40 purpose particles and obtains bifunctional catalyst E, wherein the weight percentage of each component is CuO 45%, ZnO 20%, Al
2O
33%, H-ZSM-5 32%.
[comparative example 2]
Industrial methanol dehydration catalyst CM-3-1 (modification γ-Al with the development of southwestern chemical research institute
2O
3) carry out mechanical mixture, compressing tablet, pulverizing and sieve with industrial methanol synthetic catalyst C302 and get 20～40 purpose particles and obtain bifunctional catalyst F, wherein the ratio of synthetic component of methyl alcohol and methanol dehydration component is 2/1.
[embodiment 5]
With embodiment 1～4 and comparative example 1～2 prepared catalyst A, B, C, D, E and F, in continuous-flow fixed bed compressive reaction evaluating apparatus, carry out gas-phase reaction.The loadings of catalyst: 1g.After catalyst has loaded, at logical reducing gases (5%H
2/ 95%N
2, flow velocity is 25 ml/min) condition under be warming up to 240 ℃, after reduction in 6 hours, under the condition that continues logical reducing gases, reaction bed temperature is reduced to 200 ℃, switch unstripped gas then and be warming up to 260 ℃ gradually and react.The composition of unstripped gas (volume fraction) is CO:28.9%, CO
2: 3.9%, all the other are H
2Reaction condition is pressure: 4MPa; Air speed: 1500 hours
-1System reaches balance after reacting 3 hours, then sample analysis.Online the carrying out of HP 4890D type gas chromatograph adopted in the analysis of product, uses thermal conductivity detector (TCD), carbon molecular sieve chromatogram column analysis carbon monoxide and carbon dioxide; Use hydrogen flame ionization detector, Porapak-N chromatogram column analysis methyl alcohol, dimethyl ether and hydro carbons accessory substance.The evaluation result of catalyst sees Table 1.
The reactivity worth of table 1 catalyst
| Catalyst | Carbon monoxide conversion ratio (%) | Dimethyl ether selectivity (%) | Methyl alcohol selectivity (%) | Hydrocarbon selective (%) |
| A | 95.5 | 94.2 | 5.5 | 0.33 |
| B | 94.8 | 94.5 | 5.3 | 0.19 |
| C | 93.6 | 94.4 | 5.5 | 0.06 |
| D | 93.0 | 93.6 | 6.0 | 0.4 |
| E | 95.8 | 77.8 | 7.4 | 14.8 |
| F | 80.0 | 75.5 | 24.0 | 0.5 |
By data in the table as seen, the H-ZSM-5 molecular sieve with the boron modification that adopts the present invention to make is the bifunctional catalyst of methanol dehydration component preparation, for reacting by directed preparing dimethyl ether by synthetic gas, the selectivity of dimethyl ether is greatly improved before than modification, and the growing amount of hydro carbons accessory substance reduces significantly.And compare with industrialized methanol dehydration catalyst CM-3-1, the carbon monoxide conversion ratio of catalyst of the present invention is significantly improved; It is nearly 20% that the selectivity of dimethyl ether has then improved, and obtained satisfied effect.
[embodiment 6]
3.6 gram boric acid are made into 100 milliliters boric acid aqueous solution with dissolved in distilled water, then toward wherein pouring 100 gram H-ZSM-5 molecular sieve (SiO into
2/ Al
2O
3Mol ratio=76), dipping 2 hours is after 110 ℃ of oven dry obtained the molecular sieve B-H-ZSM-5 of boron modification after spending the night again in 3 hours 500 ℃ of roastings.With above-mentioned resulting B-H-ZSM-5 is acidic components, carry out mechanical mixture, compressing tablet, pulverizing and sieve with the synthetic component of methyl alcohol and get 20～40 purpose particles and obtain bifunctional catalyst G, wherein the weight percentage of each component is CuO 47%, and ZnO 21%, H-ZSM-5 31.3%, B
2O
30.7%.
[embodiment 7]
5.1 gram boric acid are made into 100 milliliters boric acid aqueous solution with dissolved in distilled water, then toward wherein pouring 100 gram H-ZSM-11 molecular sieve (SiO into
2/ Al
2O
3Mol ratio=30), dipping 2 hours is after 110 ℃ of oven dry obtained the molecular sieve B-H-ZSM-11 of boron modification after spending the night again in 3 hours 550 ℃ of roastings.With above-mentioned resulting B-H-ZSM-11 is acidic components, carries out mechanical mixture, compressing tablet, pulverizing and sieve with the synthetic component of methyl alcohol and gets 20～40 purpose particles and obtain bifunctional catalyst H, and wherein the weight percentage of each component is CuO 45%, and ZnO 20%, Al
2O
33%, H-ZSM-5 31%, B
2O
31%.
[embodiment 8]
3.6 gram boric acid are made into 100 milliliters boric acid aqueous solution with dissolved in distilled water, then toward wherein pouring 100 gram H-ZSM-35 molecular sieve (SiO into
2/ Al
2O
3Mol ratio=50), dipping 2 hours is after 110 ℃ of oven dry obtained the molecular sieve B-H-ZSM-35 of boron modification after spending the night again in 3 hours 450 ℃ of roastings.With above-mentioned resulting B-H-ZSM-35 is acidic components, carries out mechanical mixture, compressing tablet, pulverizing and sieve with the synthetic component of methyl alcohol and gets 20～40 purpose particles and obtain bifunctional catalyst I, and wherein the weight percentage of each component is CuO 45%, and ZnO 20%, Al
2O
33%, H-ZSM-5 31.3%, B
2O
30.7%.
[embodiment 9]
3.6 gram boric acid are made into 100 milliliters boric acid aqueous solution with dissolved in distilled water, then toward wherein pouring 100 gram H-ZSM-48 molecular sieve (SiO into
2/ Al
2O
3Mol ratio=95), dipping 2 hours is after 110 ℃ of oven dry obtained the molecular sieve B-H-ZSM-48 of boron modification after spending the night again in 3 hours 500 ℃ of roastings.With above-mentioned resulting B-H-ZSM-48 is acidic components, carries out mechanical mixture, compressing tablet, pulverizing and sieve with the synthetic component of methyl alcohol and gets 20～40 purpose particles and obtain bifunctional catalyst J, and wherein the weight percentage of each component is CuO 45%, and ZnO 20%, Al
2O
33%, H-ZSM-5 31.3%, B
2O
30.7%.
[embodiment 10]
Press the operating condition of embodiment 5, check and rate catalyst G, H, I and J respectively, it the results are shown in table 2.
The reactivity worth of table 2 catalyst
| Catalyst | Carbon monoxide conversion ratio (%) | Dimethyl ether selectivity (%) | Methyl alcohol selectivity (%) | Hydrocarbon selective (%) |
| G | 91.3 | 94.6 | 5.2 | 0.2 |
| H | 95.1 | 94.8 | 5.1 | 0.1 |
| I | 94.2 | 93.8 | 5.8 | 0.4 |
| J | 92.5 | 92.9 | 6.3 | 0.8 |
Claims (8)
1, a kind of catalyst by synthesis gas one step preparation dimethyl ether comprises following component by weight percentage:
A) in the copper of cupric oxide 10～70%;
B) in the zinc of zinc oxide 5～50%;
C) silica alumina ratio SiO
2/ Al
2O
3It is 10～140 H-ZSM type zeolite 10～60%;
D) in the boron of boron oxide 0.1～10%;
E) in the aluminium of aluminium oxide 0.1～10%;
Wherein said boron adds on the H-ZSM type molecular sieve by ion-exchange, infusion process or mechanical mixing, drying and 250～750 ℃ of roastings then, thus make boron modification H-ZSM type molecular sieve as the methanol dehydration component in the catalyst.
2, according to the described catalyst of claim 1, it is characterized in that the amount of copper counts 25～50% with cupric oxide by weight percentage by synthesis gas one step preparation dimethyl ether.
3, according to the described catalyst of claim 1, it is characterized in that the amount of zinc counts 10～30% with zinc oxide by weight percentage by synthesis gas one step preparation dimethyl ether.
4, according to the described catalyst of claim 1, it is characterized in that the amount of H-ZSM type zeolite is 20～50% by weight percentage by synthesis gas one step preparation dimethyl ether.
5, according to the described catalyst of claim 1, it is characterized in that the amount of boron counts 0.5～5% with boron oxide by weight percentage by synthesis gas one step preparation dimethyl ether.
6, according to the described catalyst of claim 1, it is characterized in that H-ZSM type zeolite is selected from H-ZSM-5 by synthesis gas one step preparation dimethyl ether.
7, according to the described catalyst of claim 1, it is characterized in that the amount of aluminium counts 3～7% with aluminium oxide by weight percentage by synthesis gas one step preparation dimethyl ether.
8, according to the described catalyst of claim 1, it is characterized in that aluminium exists with the gama-alumina form by synthesis gas one step preparation dimethyl ether.
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| CN100563829C (en) * | 2008-02-03 | 2009-12-02 | 山东省科学院能源研究所 | Integral supported carbon molecular sieve catalyst and preparation method thereof is used |
| CN101747160B (en) * | 2008-11-28 | 2013-06-05 | 中国石油化工股份有限公司 | Method for preparation of methanol, dimethyl ether and low-carbon olefin with synthetic gas |
| CN102039154B (en) * | 2009-10-16 | 2013-03-20 | 中国石油化工股份有限公司 | Hydrogenation sweetening catalyst, preparing method and application thereof |
| US9610568B2 (en) * | 2012-02-15 | 2017-04-04 | Basf Se | Catalytically active body for the synthesis of dimethyl ether from synthesis gas |
| CN103657657B (en) * | 2012-08-31 | 2016-03-02 | 中国石油化工股份有限公司 | A kind of oxygenatedchemicals hydrogenation catalyst and preparation method thereof |
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| CN1153080A (en) * | 1995-12-29 | 1997-07-02 | 中国科学院兰州化学物理研究所 | Catalyst for direct preparation of dimethyl ether with synthetic gas |
| CN1063105C (en) * | 1996-10-12 | 2001-03-14 | 中国科学院新疆化学研究所 | Texturing of mixed light-hydrocarbon aromatization catalyst by solid phase reaction |
| JP2001070793A (en) * | 1999-09-08 | 2001-03-21 | Kansai Electric Power Co Inc:The | Dimethyl ether synthesis catalyst and synthesis method |
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| CN1142021C (en) * | 2000-08-11 | 2004-03-17 | 中国石油化工股份有限公司 | Catalyst for preparing dimethyl ether |
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| CN1153080A (en) * | 1995-12-29 | 1997-07-02 | 中国科学院兰州化学物理研究所 | Catalyst for direct preparation of dimethyl ether with synthetic gas |
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