CN104226352B - Butadiene catalyst made by butylene oxidation dehydrogen and method - Google Patents

Butadiene catalyst made by butylene oxidation dehydrogen and method Download PDF

Info

Publication number
CN104226352B
CN104226352B CN201310237275.2A CN201310237275A CN104226352B CN 104226352 B CN104226352 B CN 104226352B CN 201310237275 A CN201310237275 A CN 201310237275A CN 104226352 B CN104226352 B CN 104226352B
Authority
CN
China
Prior art keywords
consumption
butadiene
butylene
catalyst
catalyst made
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201310237275.2A
Other languages
Chinese (zh)
Other versions
CN104226352A (en
Inventor
吴文海
樊志贵
曾铁强
姜冬宇
缪长喜
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
Original Assignee
China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by China Petroleum and Chemical Corp, Sinopec Shanghai Research Institute of Petrochemical Technology filed Critical China Petroleum and Chemical Corp
Priority to CN201310237275.2A priority Critical patent/CN104226352B/en
Publication of CN104226352A publication Critical patent/CN104226352A/en
Application granted granted Critical
Publication of CN104226352B publication Critical patent/CN104226352B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Landscapes

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

Abstract

The present invention relates to a kind of butadiene catalyst made by butylene oxidation dehydrogen and method, mainly solve water alkene in existing preparing butadiene with butylene oxo-dehydrogenation technology higher, cause the problem that energy consumption is big, quantity of wastewater effluent is big.The present invention by using chemical composition formula is: Fe2O3·ZnO·CaO·P2O5The catalyst of M;Wherein, M is Cr2O3With selected from Eu2O3、Pm2O3、Gd2O3Or Dy2O3In the mixture of at least one rare earth oxide;By weight percentage, Fe2O3Consumption be 55~76%, the consumption of ZnO is 10 ~ 27%, and the consumption of CaO is 1 ~ 10%, P2O5Consumption be 0.01 ~ 5.0%, the consumption of M be 0.01~6.0% technical scheme preferably solve this problem, can be used in the commercial production of preparing butadiene with butylene oxo-dehydrogenation.

Description

Butadiene catalyst made by butylene oxidation dehydrogen and method
Technical field
The present invention relates to a kind of butadiene catalyst made by butylene oxidation dehydrogen and method.
Background technology
Butadiene is petrochemical industry base stock and the important monomer producing high molecular synthetic material, energy and multiple compounds Various synthetic rubber and synthetic resin are made in copolymerization.Butadiene mainly has refinery's preparing ethylene by steam cracking coproduction carbon four extracting at present Separate and two kinds of production methods of oxygenizement of butene.China's butadiene almost all derives from carbon four extracting and separates, and this process is at warp Have superiority in Ji, but to be the by-product as refinery's cracker obtain, along with the rubber industry need to butadiene yield for it Asking growth, cracker produces butadiene and has been difficult to meet needs.Butylene oxidation-dehydrogenation is the mistake with butadiene as target product Journey, the butadiene that butenc is high added value that can be used by domestic fuel, this production technology route becomes more and more important.
Mo-Bi system, Sn-P-Li system, Fe silicate system are used equally to butylene oxidation-dehydrogenation reaction.Though Mo-Bi system So water is than relatively low 6 ~ 8, but selectivity is relatively low, produces a large amount of organic oxygen-containing by-product.Sn-P-Li system activity is high, but operation Condition is the harshest, and water alkene ratio up to more than 30, energy consumption are high.Fe-series catalyst has clear advantage, as butadiene yield is high, Oxidized byproduct is few, water alkene than relatively low 12 ~ 16, current most widely used spinel-type Fe-series catalyst.
Since the butylene oxidation-dehydrogenation catalyst invention of ferrum system (USP3270080), have passed through the improvement in a lot of generation, performance is not Break and be improved.Cr3+Element can be effectively improved activity and the stability (USP3450788) of Fe series catalysts.Chinese Academy of Sciences Lanzhou Chemical Physics institute invented can be used for fluid bed butylene oxidation-dehydrogenation catalyst (CN86108152, CN96113127.6).Synthetic rubber plant of Yanshan Petrochemical company have developed for insulation fix bed chromium-free iron series B02 oxidation de- Hydrogen catalyst and the more superior B90 catalyst of performance.White wave et al. discloses the ferrum system spinel of a kind of support type and is combined Oxide butylene oxidation-dehydrogenation catalyst, has mechanical strength high, the advantage (CN92100436.2) of good stability.
Though ferrum system spinel Oxydehydrogenation catalyst commercial Application, it is high to still suffer from water alkene ratio, and energy consumption is big, waste water The problem that discharge capacity is big.Current commercial plant, including Petro-Tex company of U.S. OXD-D technique, water than condition all 12 ~ 16, so causing energy consumption big, production cost remains high.Along with the maximization of butylene oxidation device, energy-saving and emission-reduction seem more to come The most important, it is applicable to wait the low water ratio catalyst of hotbed in the urgent need to exploitation.
Summary of the invention
One of the technical problem to be solved is water alkene ratio in existing preparing butadiene with butylene oxo-dehydrogenation technology Higher, cause the problem that energy consumption is big, quantity of wastewater effluent is big, it is provided that a kind of new butadiene catalyst made by butylene oxidation dehydrogen.Should Catalyst reacts for Oxidative Dehydrogenation of Butene into Butadiene, it is possible to adapts to low-water ratio conditions, and has the feature of good stability. The two of the technical problem to be solved are to provide a kind of method of new Oxidative Dehydrogenation of Butene into Butadiene.
For solving one of above-mentioned technical problem, the technical solution used in the present invention is as follows: a kind of Oxidative Dehydrogenation of Butene fourth Diene catalyst, its chemical composition formula is:
Fe2O3·ZnO·CaO·P2O5·M
Wherein, M is Cr2O3With selected from Eu2O3、Pm2O3、Gd2O3Or Dy2O3In the mixing of at least one rare earth oxide Thing;By weight percentage, Fe2O3Consumption be 55~76%, the consumption of ZnO is 10 ~ 27%, and the consumption of CaO is 1 ~ 10%, P2O5 Consumption be 0.01 ~ 5.0%, the consumption of M is 0.01~6.0%.
In technique scheme, it is preferable that by weight percentage, Fe2O3Consumption be 55.0 ~ 70.0 %.
Preferably, by weight percentage, the consumption of ZnO is 12.0 ~ 26.0 %.
Preferably, by weight percentage, the consumption of CaO is 3.0~9.0 %.
Preferably, by weight percentage, P2O5Consumption be 0.1~4.5 %.
Preferably, by weight percentage, the consumption of M is 2.0~5.0 %.
Preferably, in mixture M, Cr2O3It is 0.05 ~ 4.0% with the weight ratio of rare earth oxide.It is highly preferred that Cr2O3With The weight ratio of rare earth oxide is 0.3 ~ 2.0%.
For solving the two of above-mentioned technical problem, the technical solution used in the present invention is as follows: a kind of Oxidative Dehydrogenation of Butene fourth The method of diene, uses and solves the catalyst that one of technical problem is described.
One is preferably carried out scheme and is, with butylene as raw material, with water as diluent, with molecular oxygen as oxidant, instead Answer temperature 320 ~ 600 DEG C, reaction pressure 0 ~ 0.4MPa, butylene volume space velocity 200 ~ 500 hours-1, H2O/ butylene volume ratio is 6 ~ 20, O2Under the conditions of/butylene volume ratio is 0.4 ~ 1.0, raw material contacts with catalyst, and reaction generates butadiene.
In technique scheme, it is preferable that reaction temperature is 360 ~ 540 DEG C.
Preferably, reaction pressure is 0.05 ~ 0.2MPa.
Preferably, butylene volume space velocity is 260 ~ 450 hours-1
Preferably, H2O/ butylene volume ratio is 8 ~ 18.
Preferably, O2/ butylene volume ratio is 0.6 ~ 0.8.
Preferably, at least one during reaction raw materials is butene-1, cis-butene-2 or trans-butene-2.
Preferably, oxidant is air or oxygen.
In the present invention, described pressure all refers to gauge pressure.
The butadiene catalyst made by butylene oxidation dehydrogen of the present invention, its preparation uses dry pigmentation, comprises the following steps:
A) by the desired amount of solid Fe2O3、ZnO、CaO、P2O5、Cr2O3, selected from Eu2O3、Pm2O3、Gd2O3Or Dy2O3In At least one rare earth oxide, and pore creating material, carry out ball milling 0.5 ~ 6 hour in ball mill, and screening is more than 150 mesh (standards Sieve) particle powder;
B) particle powder step a) obtained was 550~800 DEG C of roastings 1~36 hours, obtained described catalyst.
Wherein, solid Fe described in step a)2O3、ZnO、CaO、P2O5、Cr2O3, selected from Eu2O3、Pm2O3、Gd2O3Or Dy2O3 In at least one rare earth oxide, can by nitrate decompose obtain, it is also possible to by burning reaction obtain.
The catalyst of the present invention can be shaped to the difform catalyst such as ball, cylinder, annulus and trifolium-shaped. Catalyst pore volume 0.1 ~ 1.2cm3/ g, specific surface area 5 ~ 60m2/g.After ball milling, screening is more than 150 mesh (standard screen) particle powder, Preferably in 1 ~ 90 micrometer range.Pore creating material is selected from polyhydric alcohol such as activated carbon, high molecular polymer, glucose or plant amylums Material.The addition of pore creating material is the 0 ~ 15% of metal oxide mixture weight.Step b) sintering temperature is 550~800 DEG C, Roasting time is preferably 2 ~ 24 hours, more preferably 6 ~ 20 hours.
The a large amount of water vapour introduced during preparing butadiene with butylene oxo-dehydrogenation, relatively big mainly by specific heat of water, Control reactor temperature rise, additionally, the blast area of system deviation butylene can be made after substantial amounts of steam dilution, it is ensured that equipment safety. From the angle of catalyst performance, the existence of water vapour can promote the desorption of butadiene product, it is to avoid deep oxidation dehydrogenation, polymerization Form carbon deposit, thus improve selectivity of catalyst and stability, under low-water ratio conditions, therefore to ensure catalyst performance, It is accomplished by the desorption performance strengthening catalyst surface for product butadiene.A large number of experiments show that, in Fe-Zn-Ca-P catalytic body The cloud density of active sites can be effectively strengthened after system adds Cr and rare earth elements, so that the butadiene of electron rich Being easier to desorption, reducing by deep dehydrogenation is the probability of alkynes;Thus ensure that catalyst activity under low-water ratio conditions is with steady Qualitative.Use the present invention catalyst at 380 DEG C, butylene volume space velocity 400 hours-1, O2/C4H8It is 0.7, water alkene ratio 7 ~ 11 Under the conditions of use, conversion ratio be higher than 76%, selectivity be higher than 92%, the inactive decline of stability experiment more than 2000 hours, obtain Preferable technique effect.
Butylene dehydrogenation reaction is carried out on the flowing miniature catalyst reaction device of stainless steel reactor continuously.Product analysis uses The Organic substances such as alkene in HP-6820 gas chromatograph (TCD, FID dual detector) on-line analysis dehydrogenation product, alkadienes and The gas contents such as oxygen, carbon monoxide, carbon dioxide also calculate the conversion ratio of reaction, selectivity and yield.
Below by embodiment, the present invention is further elaborated.
Detailed description of the invention
[embodiment 1]
Take 46.0g ferrum oxide (Fe2O3), 8.0g zinc oxide (ZnO), 5.4g calcium oxide (CaO), 0.1g P2O5And 0.8g chromium oxide (Cr2O3) and 0.7gEu2O3、0.8gGd2O3Mixture, add 3.0g glucose, then in ball mill Carry out mixing 120 minutes, screening 200 mesh powder (standard screen), 700 DEG C of roastings 6 hours, obtain composite oxide catalysts A.The percentage by weight composition of gained catalyst is shown in Table 1.
[embodiment 2]
Take 24.0g ferrum oxide (Fe2O3), 10.0g zinc oxide (ZnO), 2.5g calcium oxide (CaO), 1.7g P2O5And 0.4g chromium oxide (Cr2O3) and 0.3 g Pm2O3、0.5 g Gd2O3Mixture, add 3.0g polyvinyl alcohol, then at ball Grinding machine is carried out mix 30 minutes, screening 200 mesh powder (standard screen), 700 DEG C of roastings 8 hours, obtain composite oxides and urge Agent B.The percentage by weight composition of gained catalyst is shown in Table 1.
[embodiment 3]
Take 36.2g ferrum oxide (Fe2O3), 11.0g zinc oxide (ZnO), 1.6g calcium oxide (CaO), 1.5g P2O5And 0.4g chromium oxide (Cr2O3) and 0.4 g Eu2O3、0.6 g Pm2O3、0.2 g Dy2O3Mixture, add 5.0g glucose, Then carry out mixing in ball mill 60 minutes, screening 150 mesh amount of powder (standard screen), 750 DEG C of roastings 6 hours, obtain Composite oxide catalysts C.The percentage by weight composition of gained catalyst is shown in Table 1.
[embodiment 4]
Take 52.0g ferrum oxide (Fe2O3), 10.0g zinc oxide (ZnO), 3.0g calcium oxide (CaO), 2.0g P2O5And 0.6g chromium oxide (Cr2O3) and 1.1g Pm2O3Mixture, add 9.2g activated carbon powder, then mix in ball mill Close 95 minutes, screening 200 mesh powder (standard screen), 600 DEG C of roastings 16 hours, obtain composite oxide catalysts D.Gained The percentage by weight composition of catalyst is shown in Table 1.
[embodiment 5]
Take 48.0g ferrum oxide (Fe2O3), 10.0g zinc oxide (ZnO), 3.6g calcium oxide (CaO), 2.0g P2O5And 1.0g chromium oxide (Cr2O3) and 0.6g Eu2O3Mixture, add 10.0g glucose, then mix in ball mill 60 minutes, screening > 400 mesh powder (standard screen), 650 DEG C of roastings 12 hours, obtain composite oxide catalysts E.Gained is urged The percentage by weight composition of agent is shown in Table 1.
[embodiment 6]
Take 46.0g ferrum oxide (Fe2O3), 10.0g zinc oxide (ZnO), 4.0g calcium oxide (CaO), 2.0g P2O5And 1.6g chromium oxide (Cr2O3) and 0.4g Gd2O3Mixture, add 4.5g starch, then carry out mixing 240 in ball mill Minute, screening > 200 mesh powder (standard screen), 680 DEG C of roastings 12 hours, obtain composite oxide catalysts F.Gained is catalyzed The percentage by weight composition of agent is shown in Table 1.
[embodiment 7]
Take 46.0g ferrum oxide (Fe2O3), 8.0g zinc oxide (ZnO), 5.0g calcium oxide (CaO), 0.8g P2O5And 1.6g chromium oxide (Cr2O3) and 0.4g Dy2O3Mixture, add 8.3g cellulose, then mix in ball mill 300 minutes, screening > 500 mesh powder (standard screen), 700 DEG C of roastings 10 hours, obtain composite oxide catalysts G.Gained is urged The percentage by weight composition of agent is shown in Table 1.
Table 1
[comparative example 1]
Method as disclosed in document CN86108152 prepares butylene oxidation-dehydrogenation catalyst, and catalyst consists of: ZnCr0.5Fe2O4
[embodiment 8]
Catalyst A ~ G at 380 DEG C, butylene volume space velocity 400 hours-1, O2/C4H8Being 0.7, water alkene ratio is the condition of 7 ~ 12 Under carry out performance evaluation, the results are shown in Table 2.
Table 2
Using the catalyst of the present invention, the catalyst performance under low-water ratio conditions significantly improves.
[embodiment 9]
By the condition evaluating catalyst B(embodiment 2 of [embodiment 8]) and [comparative example 1], contrast the steady of two catalyst Qualitative, catalyst performance after 2000 hours is shown in Table 3.
Table 3

Claims (10)

1. a butadiene catalyst made by butylene oxidation dehydrogen, its chemical composition formula is:
Fe2O3·ZnO·CaO·P2O5·M
Wherein, M is Cr2O3With selected from Eu2O3、Pm2O3、Gd2O3Or Dy2O3In the mixture of at least one rare earth oxide;With Percentage by weight meter, Fe2O3Consumption be 55.0~76.0%, the consumption of ZnO is 10.0 ~ 27.0%, the consumption of CaO is 1.0 ~ 10.0%, P2O5Consumption be 0.01 ~ 5.0%, the consumption of M is 0.01~6.0%.
Butadiene catalyst made by butylene oxidation dehydrogen the most according to claim 1, it is characterised in that by weight percentage, Fe2O3Consumption be 55.0 ~ 70.0 %.
Butadiene catalyst made by butylene oxidation dehydrogen the most according to claim 1, it is characterised in that by weight percentage, The consumption of ZnO is 12.0 ~ 26.0 %.
Butadiene catalyst made by butylene oxidation dehydrogen the most according to claim 1, it is characterised in that by weight percentage, The consumption of CaO is 3.0 ~ 9.0 %.
Butadiene catalyst made by butylene oxidation dehydrogen the most according to claim 1, it is characterised in that by weight percentage, P2O5Consumption be 0.1 ~ 4.5 %.
Butadiene catalyst made by butylene oxidation dehydrogen the most according to claim 1, it is characterised in that by weight percentage, M Consumption be 2.0 ~ 5.0 %.
Butadiene catalyst made by butylene oxidation dehydrogen the most according to claim 1, it is characterised in that in mixture M, Cr2O3With The weight ratio of rare earth oxide is 0.05 ~ 4.0%.
Butadiene catalyst made by butylene oxidation dehydrogen the most according to claim 7, it is characterised in that in mixture M, Cr2O3With The weight ratio of rare earth oxide is 0.3 ~ 2%.
9. the method for an Oxidative Dehydrogenation of Butene into Butadiene, it is characterised in that use the arbitrary described catalysis of claim 1 ~ 8 Agent.
The method of Oxidative Dehydrogenation of Butene into Butadiene the most according to claim 9, it is characterised in that with butylene as raw material, with Water is diluent, with molecular oxygen as oxidant, at reaction temperature 320 ~ 600 DEG C, reaction pressure 0 ~ 0.4MPa, butylene volume space velocity 200 ~ 500 hours-1, H2O/ butylene volume ratio is 6 ~ 20, O2Under the conditions of/butylene volume ratio is 0.4 ~ 1.0, raw material connects with catalyst Touching, reaction generates butadiene.
CN201310237275.2A 2013-06-17 2013-06-17 Butadiene catalyst made by butylene oxidation dehydrogen and method Active CN104226352B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201310237275.2A CN104226352B (en) 2013-06-17 2013-06-17 Butadiene catalyst made by butylene oxidation dehydrogen and method

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201310237275.2A CN104226352B (en) 2013-06-17 2013-06-17 Butadiene catalyst made by butylene oxidation dehydrogen and method

Publications (2)

Publication Number Publication Date
CN104226352A CN104226352A (en) 2014-12-24
CN104226352B true CN104226352B (en) 2016-12-28

Family

ID=52215774

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201310237275.2A Active CN104226352B (en) 2013-06-17 2013-06-17 Butadiene catalyst made by butylene oxidation dehydrogen and method

Country Status (1)

Country Link
CN (1) CN104226352B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107537512B (en) * 2016-06-29 2019-08-06 中国石油化工股份有限公司 Butadiene catalyst made by butylene oxidation dehydrogen and method

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1033013A (en) * 1986-11-27 1989-05-24 锦州石油化工公司锦州炼油厂 Butylene oxidation-dehydrogenation catalyst
EP1918312A1 (en) * 2006-10-31 2008-05-07 Ineos Europe Limited Diene polymerisation
CN102974357A (en) * 2011-09-06 2013-03-20 北京中石润达科技发展有限公司 Lattice oxygen catalyst used for preparing butadiene through butylene oxidative dehydrogenation, and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1033013A (en) * 1986-11-27 1989-05-24 锦州石油化工公司锦州炼油厂 Butylene oxidation-dehydrogenation catalyst
EP1918312A1 (en) * 2006-10-31 2008-05-07 Ineos Europe Limited Diene polymerisation
CN102974357A (en) * 2011-09-06 2013-03-20 北京中石润达科技发展有限公司 Lattice oxygen catalyst used for preparing butadiene through butylene oxidative dehydrogenation, and preparation method thereof

Also Published As

Publication number Publication date
CN104226352A (en) 2014-12-24

Similar Documents

Publication Publication Date Title
CN103769152B (en) The catalyst for phenylethylene dehydrogenation of the low water ratio of high activity, preparation method and application thereof
CN103769151B (en) High activity ethylbenzene dehydrogenation catalyst with low water ratio and preparation method thereof
CN103086828B (en) The method of volume increase divinyl
CN107537533B (en) Catalyst and its process for Oxidative Dehydrogenation of Butene into Butadiene under low-water ratio conditions
CN104226351B (en) Butadiene catalyst made by butylene oxidation dehydrogen preparation method
CN102371161B (en) Ethylbenzene dehydrogenation catalyst with low steam-to-oil ratio and preparation method thereof
CN101993336B (en) Method for preparing vinyl benzene from ethylbenzene dehydrogenation under low water ratio condition
CN106582686A (en) Ethylbenzene dehydrogenation catalyst with high activity and low steam-to-oil ratio and preparing method thereof
CN101992094B (en) Low-water-ratio ethylbenzene dehydrogenation catalyst and preparation method thereof
CN107537535A (en) Catalyst for Oxidative Dehydrogenation of Butene into Butadiene under low-water ratio conditions and preparation method thereof and process
CN100453174C (en) Low-water ratio alkyl aromatics dehydrogenation catalyst
CN101623642B (en) Ethylbenzene dehydrogenation catalyst with low water ratio
CN104226350B (en) Iron system spinel composite oxide catalysts and application thereof
CN104226352B (en) Butadiene catalyst made by butylene oxidation dehydrogen and method
CN104275201B (en) Butylene oxidation-dehydrogenation catalyst and method thereof
CN107970954A (en) Catalyst for Oxidative Dehydrogenation of Butene into Butadiene and preparation method thereof
CN103964996B (en) The power-economizing method of Oxidative Dehydrogenation of Butene into Butadiene
CN107537512B (en) Butadiene catalyst made by butylene oxidation dehydrogen and method
CN106582827A (en) High activity and low water ratio ethylbenzene dehydrogenation catalyst
CN102372592B (en) Method for preparing styrene by dehydrogenating ethylbenzene
CN102000587B (en) Catalyst for methyl ethylbenzene dehydrogenation to prepare alpha methyl styrene
CN111054353A (en) Catalyst for preparing butadiene by oxidative dehydrogenation of butylene
CN102040463B (en) Method for preparing styrene by ethylbenzene dehydrogenation
CN107537528A (en) Catalyst and its application for Oxidative Dehydrogenation of Butene into Butadiene under low-water ratio conditions
CN100460069C (en) Production of phenylethylene catalyst by low-water ratio ethylbenzene dehydrogenation

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant